CN112390735B - 烯丙基腈类化合物的制备方法 - Google Patents
烯丙基腈类化合物的制备方法 Download PDFInfo
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- CN112390735B CN112390735B CN201910759435.7A CN201910759435A CN112390735B CN 112390735 B CN112390735 B CN 112390735B CN 201910759435 A CN201910759435 A CN 201910759435A CN 112390735 B CN112390735 B CN 112390735B
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- -1 allyl nitrile compound Chemical class 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 122
- 238000006243 chemical reaction Methods 0.000 claims abstract description 115
- 238000000034 method Methods 0.000 claims abstract description 102
- 239000002904 solvent Substances 0.000 claims abstract description 63
- 238000006467 substitution reaction Methods 0.000 claims abstract description 48
- 239000012634 fragment Substances 0.000 claims abstract description 36
- 239000003446 ligand Substances 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- 239000010949 copper Substances 0.000 claims abstract description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
- 238000007333 cyanation reaction Methods 0.000 claims abstract description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 214
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 141
- 125000000217 alkyl group Chemical group 0.000 claims description 69
- 229910052736 halogen Inorganic materials 0.000 claims description 57
- 150000002367 halogens Chemical class 0.000 claims description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 55
- 229910052799 carbon Inorganic materials 0.000 claims description 55
- 125000005842 heteroatom Chemical group 0.000 claims description 42
- 125000003118 aryl group Chemical group 0.000 claims description 41
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 40
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 34
- 125000001072 heteroaryl group Chemical group 0.000 claims description 30
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 27
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 24
- 125000006239 protecting group Chemical group 0.000 claims description 24
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 19
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 18
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 15
- 239000011737 fluorine Substances 0.000 claims description 15
- 229910052731 fluorine Inorganic materials 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 13
- 125000000304 alkynyl group Chemical group 0.000 claims description 12
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 11
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 11
- 125000000746 allylic group Chemical group 0.000 claims description 10
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 10
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 10
- 125000001624 naphthyl group Chemical group 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 9
- 125000005724 cycloalkenylene group Chemical group 0.000 claims description 9
- 238000003682 fluorination reaction Methods 0.000 claims description 9
- 125000004043 oxo group Chemical group O=* 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000005466 alkylenyl group Chemical group 0.000 claims description 6
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 6
- 125000005561 phenanthryl group Chemical group 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 0.000 claims description 5
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 5
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 150000008282 halocarbons Chemical class 0.000 claims description 5
- 150000002825 nitriles Chemical class 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- YOBCNSPOCAOTDR-UHFFFAOYSA-L copper acetonitrile trifluoromethanesulfonate Chemical compound [Cu++].CC#N.CC#N.CC#N.CC#N.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F YOBCNSPOCAOTDR-UHFFFAOYSA-L 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229940124530 sulfonamide Drugs 0.000 claims description 3
- QERYCTSHXKAMIS-UHFFFAOYSA-N thiophene-2-carboxylic acid Chemical compound OC(=O)C1=CC=CS1 QERYCTSHXKAMIS-UHFFFAOYSA-N 0.000 claims description 3
- SOZFIIXUNAKEJP-UHFFFAOYSA-N 1,2,3,4-tetrafluorobenzene Chemical compound FC1=CC=C(F)C(F)=C1F SOZFIIXUNAKEJP-UHFFFAOYSA-N 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 2
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- 125000005725 cyclohexenylene group Chemical group 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003456 sulfonamides Chemical group 0.000 claims description 2
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 claims 1
- PYKWSBJYKVAEJS-UHFFFAOYSA-N formic acid;thiophene Chemical compound OC=O.C=1C=CSC=1 PYKWSBJYKVAEJS-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 8
- 125000000524 functional group Chemical group 0.000 abstract description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 348
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 180
- 230000014759 maintenance of location Effects 0.000 description 122
- 238000001514 detection method Methods 0.000 description 112
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 76
- 238000005160 1H NMR spectroscopy Methods 0.000 description 76
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- 238000004440 column chromatography Methods 0.000 description 65
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- 239000012263 liquid product Substances 0.000 description 44
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- 239000000047 product Substances 0.000 description 26
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- 125000002950 monocyclic group Chemical group 0.000 description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 9
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- 239000007788 liquid Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- GTCAXTIRRLKXRU-UHFFFAOYSA-N methyl carbamate Chemical compound COC(N)=O GTCAXTIRRLKXRU-UHFFFAOYSA-N 0.000 description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000007306 functionalization reaction Methods 0.000 description 4
- 125000004366 heterocycloalkenyl group Chemical group 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 125000002619 bicyclic group Chemical group 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
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- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 3
- 125000003088 (fluoren-9-ylmethoxy)carbonyl group Chemical group 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
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- 239000002585 base Substances 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- QMMFVYPAHWMCMS-UHFFFAOYSA-N dimethyl monosulfide Natural products CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
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- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N methanesulfonic acid Substances CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 2
- 125000004092 methylthiomethyl group Chemical group [H]C([H])([H])SC([H])([H])* 0.000 description 2
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000006574 non-aromatic ring group Chemical group 0.000 description 2
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- 239000012265 solid product Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 2
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 2
- LEIMLDGFXIOXMT-UHFFFAOYSA-N trimethylsilyl cyanide Chemical compound C[Si](C)(C)C#N LEIMLDGFXIOXMT-UHFFFAOYSA-N 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OUKYRKPPQMHVGV-UHFFFAOYSA-N (1,1,1-trichloro-2-methylpropan-2-yl)carbamic acid Chemical compound ClC(Cl)(Cl)C(C)(C)NC(O)=O OUKYRKPPQMHVGV-UHFFFAOYSA-N 0.000 description 1
- HCWFSTVHCVXYEE-UHFFFAOYSA-N (2,4-dimethylphenyl)carbamothioic S-acid Chemical compound CC1=C(C=CC(=C1)C)NC(O)=S HCWFSTVHCVXYEE-UHFFFAOYSA-N 0.000 description 1
- WTKQMHWYSBWUBE-UHFFFAOYSA-N (3-nitropyridin-2-yl) thiohypochlorite Chemical compound [O-][N+](=O)C1=CC=CN=C1SCl WTKQMHWYSBWUBE-UHFFFAOYSA-N 0.000 description 1
- HVLVVLDGZLLRBJ-UHFFFAOYSA-N (4-methoxyphenyl)methylcarbamic acid Chemical compound COC1=CC=C(CNC(O)=O)C=C1 HVLVVLDGZLLRBJ-UHFFFAOYSA-N 0.000 description 1
- BARIXIAOHBOXQD-UHFFFAOYSA-N (4-methylsulfinylphenyl)methylcarbamic acid Chemical compound CS(=O)C1=CC=C(CNC(O)=O)C=C1 BARIXIAOHBOXQD-UHFFFAOYSA-N 0.000 description 1
- QEJZCKJXVYGWMY-UHFFFAOYSA-N (cyclopentyldisulfanyl)cyclopentane Chemical compound C1CCCC1SSC1CCCC1 QEJZCKJXVYGWMY-UHFFFAOYSA-N 0.000 description 1
- SJUAOCARXAKPKI-UHFFFAOYSA-N 1,2-benzoxazol-5-ylmethylcarbamic acid Chemical compound OC(=O)NCC1=CC=C2ON=CC2=C1 SJUAOCARXAKPKI-UHFFFAOYSA-N 0.000 description 1
- FJANNOJSTOGZHK-UHFFFAOYSA-N 1-adamantyl carbamate Chemical compound C1C(C2)CC3CC2CC1(OC(=O)N)C3 FJANNOJSTOGZHK-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- LJCZNYWLQZZIOS-UHFFFAOYSA-N 2,2,2-trichlorethoxycarbonyl chloride Chemical compound ClC(=O)OCC(Cl)(Cl)Cl LJCZNYWLQZZIOS-UHFFFAOYSA-N 0.000 description 1
- QPLJYAKLSCXZSF-UHFFFAOYSA-N 2,2,2-trichloroethyl carbamate Chemical compound NC(=O)OCC(Cl)(Cl)Cl QPLJYAKLSCXZSF-UHFFFAOYSA-N 0.000 description 1
- PXVUDLXXKGSXHH-UHFFFAOYSA-N 2,4,6-trimethoxybenzenesulfonamide Chemical compound COC1=CC(OC)=C(S(N)(=O)=O)C(OC)=C1 PXVUDLXXKGSXHH-UHFFFAOYSA-N 0.000 description 1
- 125000001917 2,4-dinitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C(=C1*)[N+]([O-])=O)[N+]([O-])=O 0.000 description 1
- YJRISODHEYGPEL-UHFFFAOYSA-N 2,6-dimethoxy-4-methylbenzenesulfonamide Chemical compound COC1=CC(C)=CC(OC)=C1S(N)(=O)=O YJRISODHEYGPEL-UHFFFAOYSA-N 0.000 description 1
- DWKLSWPFGOTZII-UHFFFAOYSA-N 2-(1-adamantyl)propan-2-yl carbamate Chemical compound C1C(C2)CC3CC2CC1(C(C)(OC(N)=O)C)C3 DWKLSWPFGOTZII-UHFFFAOYSA-N 0.000 description 1
- VPVFQDMANSFAHW-UHFFFAOYSA-N 2-(3,5-ditert-butylphenyl)propan-2-ylcarbamic acid Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(C(C)(C)NC(O)=O)=C1 VPVFQDMANSFAHW-UHFFFAOYSA-N 0.000 description 1
- 125000003821 2-(trimethylsilyl)ethoxymethyl group Chemical group [H]C([H])([H])[Si](C([H])([H])[H])(C([H])([H])[H])C([H])([H])C(OC([H])([H])[*])([H])[H] 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
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- 239000013064 chemical raw material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
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- 239000004210 ether based solvent Substances 0.000 description 1
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- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000012035 limiting reagent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- HNQIVZYLYMDVSB-UHFFFAOYSA-N methanesulfonimidic acid Chemical compound CS(N)(=O)=O HNQIVZYLYMDVSB-UHFFFAOYSA-N 0.000 description 1
- BAYDZXVPEQFLCZ-UHFFFAOYSA-N n-(2-trimethylsilylethoxy)methanamine Chemical compound CNOCC[Si](C)(C)C BAYDZXVPEQFLCZ-UHFFFAOYSA-N 0.000 description 1
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- 238000005457 optimization Methods 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
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- NIXKBAZVOQAHGC-UHFFFAOYSA-N phenylmethanesulfonic acid Chemical compound OS(=O)(=O)CC1=CC=CC=C1 NIXKBAZVOQAHGC-UHFFFAOYSA-N 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- OCAAZRFBJBEVPS-UHFFFAOYSA-N prop-2-enyl carbamate Chemical compound NC(=O)OCC=C OCAAZRFBJBEVPS-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
- BZVJOYBTLHNRDW-UHFFFAOYSA-N triphenylmethanamine Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(N)C1=CC=CC=C1 BZVJOYBTLHNRDW-UHFFFAOYSA-N 0.000 description 1
- LVLANIHJQRZTPY-UHFFFAOYSA-N vinyl carbamate Chemical compound NC(=O)OC=C LVLANIHJQRZTPY-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
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- C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
- C07C255/34—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring with cyano groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by unsaturated carbon chains
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- C07C255/35—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by halogen atoms, or by nitro or nitroso groups
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- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
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- C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
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- C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D211/72—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, directly attached to ring carbon atoms
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- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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Abstract
本发明公开了一种烯丙基腈类化合物的制备方法。本发明的制备方法包括以下步骤：溶剂中，在铜催化剂、双噁唑啉配体和所述的如式A所示的化合物的存在下，将含有如式II所示的结构片段的烯丙基化合物与如式III所示的氰基化试剂进行如下式的取代反应，得到含有如式I所示的结构片段的烯丙基腈类化合物。该方法收率高、底物普适性广、官能团兼容性好，且具有反应条件温和和操作简单的特点。
Description
技术领域
本发明涉及一种烯丙基氰类化合物的制备方法。
背景技术
烯烃是一种简单易得的化工原料，并且烯烃片段广泛存在于天然产物和活性分子中，由于烯烃双键本身的反应活性较高，容易发生多种化学反应。对于不对成的烯烃化合物，烯丙位碳氢键不对称官能化反应则可以保留烯烃双键的同时，直接在烯烃底物上引入手性官能团，丰富烯烃的转化类型，得到的产物可以进一步转化成其他产物，因此，烯丙位碳氢键不对称官能化反应的发展对于烯烃的转化有着重要意义[(a)Covell,D.J.；White,M.C.A.Angew.Chem.Int.Ed.2008,47,6448.(b)Bayeh,L.；Le,P.Q.；Tambar,U.K.Nature2017,547,196]。另外，双键片段广泛存在于天然产物和活性药物分子中，烯丙位碳氢键不对称官能化反应可以直接用于这些复杂分子的后期修饰当中，这对于构建潜在药物分子化合物库具有重要意义。
尽管烯丙位碳氢键不对称官能化反应在合成具有重要意义，其发展还是很缓慢的。早在1958年，Kharasch等人报道了首例铜催化的烯丙位碳氢键氧化反应(Kharasch,M.S.；Sosnovsky,G.J.Am.Chem.Soc.1958,80,756)：
此后几十年，人们通过手性配体的优化，以较高的对映选择性实现了相应的不对称反应(Eames,J.；Watkinson,M.Angew.Chem.Int.Ed.2001,40,3567)。
Scheme3.Allylic oxidation of cycloalkenes using a C2-symmetric bis(oxazoline)ligand5：
a)PhCO3t Bu，CuOTf(5mol％），chiral ligand 5a-e(6-8mol％)；OTf＝trifluoromethane-sulfonate
但是其依然制备的是烯丙位碳氧类化合物，而且在效率方面依旧存在很大的问题。首先，该反应必须使用过量的烯烃底物，而将氧化剂作为限制试剂，为了获得较好的对应选择性，反应通常在低温下需要进行数天，效率很低。其次，该反应底物受限，一般只能适用于环己烯、环庚烯等简单烯烃作为反应底物，对于开链烯烃，以及复杂的烯烃，该反应一般不适用。显然，这个反应是不能适用与烯烃的高效转化和药物分子的后期修饰当中的。
因此，本领域急需一种能高效简单地实现烯丙位碳氢键的氰基化反应的方法。
发明内容
本发明所要解决的技术问题是为了克服现有技术中烯丙位碳氢键反应收率低、种类单一、底物普适性差以及官能团兼容性差的缺陷，而提供了一种烯丙基腈类化合物的制备方法。本发明的方法收率高、底物普适性广、官能团兼容性好，而且还具有反应条件温和和操作简单。
本发明是通过下述技术方案来解决上述技术问题的。
本发明提供了一种如式A所示的化合物：
其中，R1a、R1b和R1c各自独立地为C1～C4烷基或者苯基；
R2a为C6～C14芳基或被一个或多个R2a-1取代的C6～C14芳基；
R2a-1为卤素、C1～C4烷基、卤素取代的C1～C4烷基、C1～C4烷氧基或C6～C14芳基；当R2a-1为多个时，R2a-1相同或者不同。
式A中，当R1a、R1b和R1c各自独立地为C1～C4烷基，所述的C1～C4烷基可以为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基，还可以为甲基。
式A中，当R2a为C6～C14芳基时，所述的C6～C14芳基可以为苯基、萘基、蒽基或菲基，还可以为苯基或萘基
式A中，当R2a为R2a-1取代的C6～C14芳基时，所述的R2a-1可以为1个。
式A中，当R2a为R2a-1取代的C6～C14芳基时，所述的C6～C14芳基可以为苯基、萘基、蒽基或菲基，还可以为苯基。
式A中，当R2a为R2a-1取代的C6～C14芳基时，所述的R2a-1取代的C6～C14芳基“甲基、叔丁基、苯基、氟、氯或三氟甲基”取代的苯基，进一步可以为
式A中，当R2a-1为卤素时，所述的卤素可以为氟、氯、溴或碘，还可以为氟或氯。
式A中，当R2a-1为C1～C4烷基时，所述的C1～C4烷基可以为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基，还可以为甲基或叔丁基。
式A中，当R2a-1为卤素取代的C1～C4烷基时，所述的卤素取代的C1～C4烷基可以为三氟甲基。
式A中，当R2a-1为C1～C4烷氧基时，所述的C1～C4烷氧基可以为甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基或叔丁氧基，还可以为甲氧基。
式A中，当R2a-1为C6～C14芳基时，所述的C6～C14芳基可以为苯基、萘基、蒽基或菲基，还可以为苯基。
在本发明某一实施方案中，式A中，R2a-1为卤素或卤素取代的C1～C4烷基。
在本发明某一实施方案中，式A中，当R2a为R2a-1取代的C6～C14芳基时，R2a-1位于磺酰胺的对位。
在本发明某一实施方案中，式A中，
为
在本发明某一实施方案中，式A中，R2a为
在本发明某一实施方案中，如式A所示的化合物为如下任一化合物：
在本发明某一实施方案中，如式A所示的化合物为如下任一化合物：
本发明还提供了一种上述的如式A所示的化合物的制备方法，其包括以下步骤：有机溶剂中，在碱存在下，将如式B所示的化合物和氟化试剂进行如下所示的氟化反应，制得所述的如式A所示的化合物；
所述的氟化反应的条件和操作可以为本领常规的条件和操作，本发明特别优选以下条件和操作：
所述的有机溶剂可为本领域此类反应常规的溶剂，优选卤代烷烃类溶剂。所述的卤代烷烃类溶剂优选二氯甲烷。
所述的碱可以为本领域常规的碱，优选NaH。所述的碱与所述的如式A所示的化合物的摩尔比可以为1:1～3：1(例如2：1)。
所述的氟化试剂可以为N-氟代双苯磺酰胺(NFSI)。所述的氟化试剂与所述的如式A所示的化合物的摩尔比可以为1:1～5：1(例如4：1)。
所述的氟化反应的温度可为本领域此类反应常规的温度，优选0℃。
所述的氟化反应的进行可按照本领域常规的检测方法(例如TLC、GC、HPLC或HNMR等)进行监测，一般以如式B所示的化合物消失时作为反应的终点。所述的氟化反应的时间优选6小时。
本发明还提供了一种烯丙基腈类化合物的制备方法，其包括以下步骤：溶剂中，在铜催化剂、双噁唑啉配体和所述的如式A所示的化合物的存在下，将含有如式II所示的结构片段的烯丙基化合物与如式III所示的氰基化试剂进行如下式的取代反应，得到含有如式I所示的结构片段的烯丙基腈类化合物即可；
其中，用*标注的碳是指S构型手性碳、R构型手性碳或非手性碳；R3a、R3b和R3c各自独立地为C1～C4烷基。
式III中，当R3a、R3b和R3c独立地为C1～C4烷基，所述的C1～C4烷基可以为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基，还可以为甲基。
所述的取代反应中，所述的溶剂可以为芳烃类溶剂、取代芳烃类溶剂、腈类溶剂、卤代烃类溶剂、醚类溶剂、酮类溶剂、酯类溶剂和酰胺类溶剂中的一种或多种。所述的芳烃类溶剂可以为苯。所述的取代芳烃类溶剂可以为氯苯、溴苯、氟苯、三氟甲苯、四氟苯、六氟苯和三氟甲基苯中的一种或多种，还可以为六氟苯。所述的腈类溶剂可以为乙腈。所述的卤代烃类溶剂可以为二氯甲烷(DCM)。所述的醚类溶剂可以为四氢呋喃。所述的酮类溶剂可以为丙酮。所述的酯类溶剂可以为乙酸乙酯。所述的酰胺类溶剂可以为N,N-二甲基甲酰胺(DMF)。所述的溶剂的用量可以不做具体的限定，只要不影响反应进行即可。所述的溶剂可以经过无水处理(无水处理的操作和和方法为本领域常规的操作和方法)。
所述的取代反应中，所述的铜催化剂可以为铜粉、碘化亚铜、氯化亚铜、溴化亚铜、氧化亚铜、醋酸亚铜、三氟甲磺酸亚铜和苯的复合物(三氟甲磺酸亚铜和苯的比例为2:1)、噻吩甲酸亚铜、溴化亚铜和二甲硫醚复合物、四乙腈六氟磷酸铜、四乙腈三氟甲磺酸铜、四乙腈四氟硼酸铜、氯化铜、溴化铜、氟化铜、醋酸铜和三氟甲磺酸铜中的一种或多种，又可以为溴化亚铜、噻吩甲酸亚铜、四乙腈六氟磷酸铜、四乙腈三氟甲磺酸铜和醋酸亚铜中的一种或多种，还可以为醋酸亚铜。
所述的取代反应中，所述的铜催化剂的用量可为本领域常规的用量。所述的铜催化剂的用量优选为所述的含有如式II所示结构片段的烯丙基化合物的1～50％摩尔当量，还可以为1～10％摩尔当量，例如5％摩尔当量。
所述的取代反应中，所述的双噁唑啉配体可以为
和/或
其中R4a、R4b、R5a和R5b独立为氢、C1～C4烷基、或卤素取代的C1～C4烷基，
或者，“R4a和R4b”或“R5a和R5b”与其相连的碳一起形成的C3～C7环烷基(例如环丙基、环丁基、环戊基、环己基、环庚基)。
所述的双噁唑啉配体中，“R4a和R4b”或“R5a和R5b”与其相连的碳一起形成的C3～C7环烷基，进一步可以为
和/或
所述的取代反应中，所述的双噁唑啉配体的用量可以为本领域常规的用量。所述的双噁唑啉配体的用量优选为所述的含有如式II所示结构片段的烯丙基化合物的1～75％摩尔当量，例如7.5％摩尔当量。
所述的取代反应中，所述的铜催化剂与所述的双噁唑啉配体的摩尔比可以为本领常规的摩尔比，优选2.0:1～1.0:3，例如1:1.5。
所述的取代反应中，所述的含有如式II所示结构片段的烯丙基化合物的浓度可以为本领域常规的浓度，优选0.01～1.00mol/L，还可以优选为0.01～0.20mol/L。
所述的取代反应中，所述的如式A所示的化合物与所述的含有如式II所示结构片段的烯丙基化合物的摩尔比可以为1.0:1～4.0:1，还可以优选为2.5:1～3.0:1。
所述的取代反应中，所述的如式III所示的氰基化试剂与所述的含有如式II所示结构片段的烯丙基化合物的摩尔比可以为1.0:1～5.0:1，还可以为2.0:1～3.0:1。
所述的取代反应的温度可以为0～80℃，还可以为0～30℃。
所述的取代反应还可以在保护气体下进行。所述的保护气体可以为氮气和/或氩气。
所述的取代反应的进程可以采用本领域常规的检测方法(例如TLC、HPLC、HNMR)进行监测，优选以所述的含有如式II所示结构片段的烯丙基化合物消失或者不再反应作为反应的终点。所述的取代反应的时间可以为1～36小时。
在本发明某一实施方案中，当所述的双噁唑啉配体为
时，得到的如式I所示的结构片段的烯丙基腈类化合物
其中，用*标注的碳是R构型手性碳。
在本发明某一实施方案中，当所述的双噁唑啉配体为
时，得到的如式I所示的结构片段的烯丙基腈类化合物
其中，用*标注的碳是S构型手性碳。
在本发明某一实施方案中，所述的双噁唑啉配体为
和/或
所述的如式A所示的氧化剂为
中的一种或多种。
在本发明某一实施方案中，所述的含有如式II所示的结构片段的烯丙基化合物如式II’所示，相应地得到如式I’所示的含有所述的如式I所示的结构片段的烯丙基腈类化合物；
其中，R1、R2、R3和R4独立地为氢、卤素、C1～C20烷基、R1-1取代的C1～C20烷基、C2～C10烯基、C2～C10炔基、R1-2取代的C2～C10炔基、C3～C30环烷基、R1-3取代的C3～C30环烷基、C3～C30杂环烷基、R1-4取代的C3～C30杂环烷基、C6～C30芳基、R1-5取代的C6～C30芳基、C1～C30杂芳基、R1-6取代的C1～C30杂芳基、OR1-7、-SiMe2Ph、-SiPh3、
-(P＝O)Ph2或-NPhth；所述的C3～C30杂环烷基、所述的R1-4取代的C3～C30杂环烷基、所述的C1～C30杂芳基和R1-6取代的C1～C30杂芳基中的杂原子独立地为N、O和S中的一种或多种，杂原子数为1～3个；
R1-1、R1-2、R1-3、R1-4、R1-5和R1-6独立地为卤素、-OR1-1-1、-NPhth、-N3、-O(C＝O)R1-1-2、-(C＝O)Ph3、-(C＝O)OR1-1-3、C1～C4烷基、卤素取代的C1～C4烷基、-SCF3、卤素取代的C1～C4烷氧基、C1～C4烷氧基、C3～C10杂芳基、-NR1-1-4或-SiPh3；所述的C3～C10杂芳基的杂原子为N、O和S中的一种或多种，杂原子数为1～3个；R1-7为羟基保护基团；R1-1、R1-2、R1-3、R1-4、R1-5和R1-6独立地为1个或多个，当R1-1、R1-2、R1-3、R1-4、R1-5和R1-6独立地为多个时，R1-1、R1-2、R1-3、R1-4、R1 -5和R1-6独立地相同或不同；
R1-1-1为羟基保护基团；R1-1-2为C1～C4烷基或苯基取代的C1～C4烷基；R1-1-3为C1～C4烷基或
R1-1-4为氨基保护基团；R1-1-4为1个或多个，当R1-1-4为多个时，R1-1-4相同或不同；
或者，“R1和R2”、或、“R3和R4”与其相连的碳一起形成C3～C30环烷基、氧代的C3～C30环烯基、C3～C30杂环烷基、R2-1取代的C3～C30杂环烷基、
所述的C3～C30杂环烷基和R2-1取代的C3～C30杂环烷基的中杂原子独立地为N、O和S中的一种或多种，杂原子数为1～3个；
R2-1为氧代、氨基保护基团(当C3～C30杂环烷基中的杂原子为N，氨基保护基与C3～C30杂环烷基中的杂原子N链接)或苯基；R2-1为1个或多个，当R2-1为多个时，R2-1相同或不同；
或者，“R1和R3”、“R1和R4”、“R2和R3”、或、“R2和R4”与其相连的碳一起形成C3～C30亚环烯基、R3-1取代的C3～C30亚环烯基、C3～C30亚杂环烯基、
所述C3～C30杂环烯基中的杂原子独立地为N、O和S中的一种或多种，杂原子数为1～3个；
R2-1为氧代或羟基保护基团。
其中，当R1和R2独立地为卤素时，所述的卤素可以为氟、氯、溴或碘，还可以为氟或溴。
其中，当R1、R2、R3和R4独立地为C1～C20烷基时，所述的C1～C20烷基可以为C1～C4烷基，进一步可以为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基，进一步还可以为甲基、乙基、正丙基或正丁基。
其中，当R1和R2独立地为R1-1取代的C1～C20烷基时，所述的C1～C20烷基的可以为C1～C4烷基，进一步可以甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基，还可以进一步为甲基或乙基。
其中，当R1和R2独立地为R1-1取代的C1～C20烷基时，所述的R1-1取代的C1～C20烷基可以为“-NPhth、羟基保护基团、氨基保护基团、-(C＝O)Ph3或-SiPh3”取代的C1～C4烷基，进一步可以为
其中，当R4独立地为R1-1取代的C1～C20烷基时，所述的C1～C20烷基可以为C1～C12烷基，进一步可以为甲基、乙基或正十二烷基。
其中，当R4为R1-1取代的C1～C20烷基时，所述的C1～C20烷基可以为C1～C12烷基，进一步可以为乙基或正十二烷基。
其中，当R4为R1-1取代的C1～C20烷基时，所述的R1-1取代的C1～C20烷基可以为“C1～C4烷基、-N3、羟基保护基团、-NPhth、卤素、-O(C＝O)R1-1-2或-(C＝O)OR1-1-3”取代的C1～C12烷基，进一步可以为
其中，当R4为C2～C10烯基时，所述的C2～C10烯基可以为C2～C4烯基，进一步可以为
其中，当R4为R1-3取代的C2～C10炔基时，所述的C2～C10炔基可以为C2～C4炔基，进一步可以为乙炔基。
其中，当R4为R1-3取代的C2～C10炔基时，所述的R1-3取代的C2～C10炔基可以“-SiPh3”取代的C2～C4炔基，进一步可以为
其中，当所述的R1和R2独立地为C3～C30环烷基，所述的C3～C30环烷基可以为C3～C6环烷基，进一步可以为环己基。
其中，当所述的R1和R2独立地为C3～C30环烷基，所述的环烷基为饱和的单环取代基。
其中，当所述的R1和R2独立地为R1-4取代的C3～C30杂环烷基时，所述的C3～C30杂环烷基中的杂原子可以为N。
其中，当所述的R1和R2独立地为R1-4取代的C3～C30杂环烷基时，所述的C3～C30杂环烷基中的杂原子的个数可以为1个。
其中，当所述的R1和R2独立地为R1-4取代的C3～C30杂环烷基时，所述的C3～C30杂环烷基可以为C3～C5杂环烷基。
其中，当所述的R1和R2独立地为R1-4取代的C3～C30杂环烷基时，所述R1-4取代的C3～C30杂环烷基可以为“氧代、苯基或氨基保护基”取代的C3～C5杂环烷基，进一步可以为
其中，当所述的R1和R2独立地为R1-4取代的C3～C30杂环烷基时，所述的杂环烷基可为单环的杂环烷基。
其中，当所述的R1和R2独立地为C6～C30芳基时，所述的C6～C30芳基可以为C6～C14芳基，进一步可以为苯基或萘基
其中，当所述的R1和R2独立地为R1-5取代的C6～C30芳基时，所述的C6～C30芳基可以为C6～C14芳基，进一步可以为苯基。
其中，当所述的R1和R2独立地为R1-5取代的C6～C30芳基时，所述的R1-5取代的C6～C30芳基可以为“卤素、羟基保护基、卤素取代的C1～C4烷基、-SCF3、卤素取代的C1～C4烷氧基、C1～C4烷氧基或C3～C10杂芳基”取代的C6～C14芳基，可以进一步为
其中，当所述的R1和R2独立地为C1～C30杂芳基，所述的C1～C30杂芳基可以为C3～C5杂芳基。
其中，当所述的R1和R2独立地为C1～C30杂芳基，所述的C1～C30杂芳基中的杂原子可以为O或S。
其中，当所述的R1和R2独立地为C1～C30杂芳基，所述的C1～C30杂芳基中的杂原子的个数可以为1个。
其中，当所述的R1和R2独立地为C1～C30杂芳基，所述的C1～C30杂芳基可以为“杂原子为O或S”的C3～C10杂芳基，进一步可以为
其中，当所述的R1和R2独立地为R1-6取代的C1～C30杂芳基时，所述的C1～C30杂芳基中的杂原子可以为S或N。
其中，当所述的R1和R2独立地为R1-6取代的C1～C30杂芳基时，所述的C1～C30杂芳基中的杂原子个数可以为1个。
其中，当所述的R1和R2独立地为R1-6取代的C1～C30杂芳基时，所述的C1～C30杂芳基可以为C3～C10杂芳基。
其中，当所述的R1和R2独立地为R1-6取代的C1～C30杂芳基时，所述的R1-6取代的C1～C30杂芳基可以为“卤素或C1～C4烷氧基”取代的C3～C10杂芳基，进一步可以为
其中，当所述的R1-1、R1-2、R1-3、R1-4、R1-5和R1-6独立地为卤素，所述的卤素为氟、氯、溴或碘。
其中，当R1-1、R1-2、R1-3、R1-4、R1-5和R1-6独立地为C1～C4烷基，所述的C1～C4烷基可以为甲基。
其中，当R1-1、R1-2、R1-3、R1-4、R1-5和R1-6独立地为卤素取代的C1～C4烷基，所述的卤素取代的C1～C4烷基可为三氟甲基。
其中，当R1-1、R1-2、R1-3、R1-4、R1-5和R1-6独立地为卤素取代的C1～C4烷氧基，所述的卤素取代的C1～C4烷氧基可为三氟甲氧基。
其中，当R1-1、R1-2、R1-3、R1-4、R1-5和R1-6独立地为C1～C4烷氧基，所述的C1～C4烷氧基可为甲氧基。
其中，当R1-1、R1-2、R1-3、R1-4、R1-5和R1-6独立地为C3～C10杂芳基时，所述的C3～C10杂芳基可以为
其中，当R1-1-1为羟基保护基或R1-7为羟基保护基团时，所述的羟基保护基团可为乙酰基(Ac-)、
其中，当R1-1-2为C1～C4烷基或苯基取代的C1～C4烷基时，所述的C1～C4烷基可以为甲基或乙基。
其中，当R1-1-3为C1～C4烷基时，所述的C1～C4烷基可以为甲基。
其中，当R1-1-4为氨基保护基团时，所述的氨基保护基团为
其中，当“R1和R2”、或、“R3和R4”与其相连的碳一起形成C3～C30环烷基时，所述的C3～C30环烷基可以为C3～C10环烷基，进一步为环己基或环庚基。
其中，当“R1和R2”、或、“R3和R4”与其相连的碳一起形成C3～C30环烷基时，所述的C3～C30环烷基可以为饱和的单环烷基。
其中，当“R1和R2”、或、“R3和R4”与其相连的碳一起形成所述的氧代的C3～C30环烯基时，所述的氧代的C3～C30环烯基可以为氧代的C3～C6环烯基，进一步可以为
其中，当“R1和R2”、或、“R3和R4”与其相连的碳一起形成所述的氧代的C3～C30环烯基时，所述的环烯基可以为单环环烯基。
其中，当“R1和R2”、或、“R3和R4”与其相连的碳一起形成R2-1取代的C3～C30杂环烷基，所述的C3～C30杂环烷基中的杂原子可以为O或N。
其中，当“R1和R2”、或、“R3和R4”与其相连的碳一起形成R2-1取代的C3～C30杂环烷基，所述的C3～C30杂环烷基中的杂原子的个数可以为1个。
其中，当“R1和R2”、或、“R3和R4”与其相连的碳一起形成R2-1取代的C3～C30杂环烷基，所述的C3～C30杂环烷基中为C3～C5杂环烷基。
其中，当“R1和R2”、或、“R3和R4”与其相连的碳一起形成R2-1取代的C3～C30杂环烷基，所述的“氧代、氨基保护基或苯基”取代的C3～C5杂环烷基，进一步
其中，当“R1和R2”、或、“R3和R4”与其相连的碳一起形成R2-1取代的C3～C30杂环烷基，所述的杂环烷基可以为单环的杂环烷基。
其中，当R2-1为氨基保护基时，所述的氨基保护基团可以为
其中，当R2-1为苯基时，所述的苯基与所述的C3～C30杂环烷基并环连接。
其中，当“R1和R3”、“R1和R4”、“R2和R3”、或、“R2和R4”与其相连的碳一起形成C3～C30亚环烯基时，所述的C3～C30亚环烯基可以为C3～C7亚环烯基，亚环己烯基或亚环庚烯基。
其中，当“R1和R3”、“R1和R4”、“R2和R3”、或、“R2和R4”与其相连的碳一起形成亚C3～C30环烯基时，所述的亚环烯基可以为单环的亚环烯基。
其中，当“R1和R3”、“R1和R4”、“R2和R3”、或、“R2和R4”与其相连的碳一起形成R3-1取代的C3～C30亚环烯基时，所述的R3-1取代的C3～C30亚环烯基可以为羟基保护基取代的C3～C7亚环烯基，进一步可以为
其中，当“R1和R3”、“R1和R4”、“R2和R3”、或、“R2和R4”与其相连的碳一起形成R3-1取代的C3～C30亚环烯基时，所述的亚环烯基可以为单环的亚环烯基。
其中，当R2-1为羟基保护基团时，所述的羟基保护基团为乙酰基。
在本发明某一实施方案中，R1和R2中，一个为氢或卤素；所述的卤素为氟。
在本发明某一实施方案中，R3为氢。
在本发明某一实施方案中，R4为C1～C20烷基或R1-1取代的C1～C20烷基。
在本发明某一实施方案中，“R3和R4”与其相连的碳一起形成C3～C30环烷基。
在本发明某一实施方案中，当R4为R1-1取代的C1～C20烷基时，R3为H；R1和R2中，其中一个为氢，另一个为C6～C30芳基；所述的R1-1不为-(C＝O)OR1-1-2。
在本发明某一实施方案中，当R4为C1～C20烷基时，R3为H；R1和R2中，其中一个为H，另一个为C6～C30芳基、R1-1取代的C1～C20烷基、-SiMe2Ph、-NPhth或R1-2取代的C2～C10炔基，所述的R1-1为-SiPh3。
在本发明某一实施方案中，当R4为C1～C20烷基时，R3为H；R1和R2中，其中一个为C1～C20烷基或卤素，另一个为C6～C30芳基；所述的卤素为氟。
在本发明某一实施方案中，当“R3和R4”与其相连的碳一起形成C3～C30环烷基时，R1和R2中，其中一个为C6～C30芳基或R1-5取代的C6～C30芳基，另一个为卤素；所述的卤素为氟。
在本发明某一实施方案中，所述的如式II’所示的含有如式II所示的结构片段的烯丙基化合物为如下任一化合物：
在本发明某一实施方案中，所述的如式I’所示的含有如式I所示的结构片段的烯丙基腈类化合物为如下任一化合物：
本发明还提供了一种上述的如式A所示的化合物作为氧化剂在氰化反应中的应用；所述的氰化反应的反应位点为烯丙位。
所述的应用中，所述的氰化反应可以用于制备上述的含有如式I所示的结构片段的烯丙基腈类化合物；
所述的应用中，所述的含有如式I所示的结构片段的烯丙基腈类化合物的制备方法同前所述。
本发明还提供一种式I’-7所示的化合物的晶型，其晶系属于单斜晶系，P21空间群，晶胞参数为
α＝γ＝90°,β＝91.5420(10)°；
定义
本发明中，“室温”是指10～30℃。
本发明中，氨基保护基团在该领域是熟知的并且包括那些详细描述于在有机合成中的保护基团(Protecting Groups in Organic Synthesis)，T.W.Greene和P.G.M.Wuts，第三版，约翰威利国际出版公司(John Wiley&Sons)，1999，通过引用结合在此。例如，氮保护基团(如酰胺基团)包括但不限于，甲酰胺，乙酰胺，以及苯甲酰胺；氮保护基团(例如氨基甲酸酯基团)包括但不限于，甲基氨基甲酸酯、乙基氨基甲酸酯、9-芴甲基氨基甲酸酯(Fmoc)、2,7-二-叔丁基-[9-(10,10-二氧代-10,10,10,10-四氢噻吨基)]甲基氨基甲酸酯(DBD-Tmoc)、4-甲氧基苯甲酰氨基甲酸酯(Phenoc)、2,2,2-三氯乙基氨基甲酸酯(Troc)、2-三甲基硅烷基乙基氨基甲酸酯(Teoc)、2-苯乙基氨基甲酸酯(hZ)、1-(1-金刚烷基)-1-甲基乙基氨基甲酸酯(Adpoc)、1,1-二甲基-2,2-二溴乙基氨基甲酸酯(DB-t-BOC)、1,1-二甲基-2,2,2-三氯乙基氨基甲酸酯(TCBOC)、1-甲基-1-(4-二苯基)乙基氨基甲酸酯(Bpoc)、1-(3,5-二-叔丁基苯基)-1-甲基乙基氨基甲酸酯(t-Bumeoc)、2-(2′-和4′-吡啶基)乙基氨基甲酸酯(Pyoc)、叔丁基氨基甲酸酯(BOC)、1-金刚烷基氨基甲酸酯(Adoc)、乙烯基氨基甲酸酯(Voc)、烯丙基氨基甲酸酯(Alloc)、1-异丙基烯丙基氨基甲酸酯(ipaoc)、肉桂基氨基甲酸酯(Coc)、4-硝基肉桂基氨基甲酸酯(Noc)、苄基氨基甲酸酯(Cbz)、对甲氧基苄基氨基甲酸酯(Moz)、4-甲基亚磺酰基苄基氨基甲酸酯(Msz)、[2-(1,3-二硫化环戊烷基)]甲基氨基甲酸酯(Dmoc)、4-甲基苯硫基氨基甲酸酯(Mtpc)、2,4-二甲基苯硫基氨基甲酸酯(Bmpc)、2-乙磷基氨基甲酸酯(Peoc)、2-三苯基异丙磷基氨基甲酸酯(Ppoc)、5-苯并异噁唑基甲基氨基甲酸酯、以及2-(三氟甲基)-6-色酮基甲基氨基甲酸酯(Tcroc)；氮保护基团(例如磺酰胺基团)包括但不限于，对-甲苯磺酰胺(Ts)，苯磺酰胺、2,3,6,-三甲基-4-甲氧基苯磺酰胺(Mtr)、2,4,6-三甲氧基苯磺酰胺(Mtb)、2,6-二甲基-4-甲氧基苯磺酰胺(Pme)、2,3,5,6-四甲基-4-甲氧基苯磺酰胺(Mte)、4-甲氧基苯磺酰胺(Mbs)、2,4,6-tri甲基苯磺酰胺(Mts)、2,6-二甲氧基-4-甲基苯磺酰胺(iMds)、2,2,5,7,8-五甲基色满-6-磺酰胺(Pmc)、甲烷磺酰胺(Ms)、β-三甲基硅烷基乙烷磺酰胺(SES)、以及4-(4′,8′-二甲氧基萘基甲基)苯磺酰胺(DNMBS)；其他氮保护基团包括但不限于，N-1,1,4,4-四甲基二甲硅烷基氮杂环戊烷加合物(STABASE)、N-[2-(三甲基甲硅烷基)乙氧基]甲胺(SEM)、N-三苯基甲胺(Tr)、N-[(4-甲氧基苯基)二苯基甲基]胺(MMTr)、N-9-苯基芴胺(PhF)、N-二茂铁基甲基氨基(Fcm)、N-亚环己基胺、N-硼烷衍生物、N-铜螯合物、N-锌螯合物、N-硝胺、N-亚硝胺、胺N-氧化物、二苯基膦胺(Dpp)、二甲基硫代膦胺(Mpt)、二苯基硫代膦胺(Ppt)、邻硝基苯亚磺酰胺(Nps)、以及3-硝基吡啶亚磺酰胺(Npys)。
本发明中，羟基保护基团在本领域是熟知的并且包括那些详细描述于在有机合成中的保护基团(Protecting Groups in Organic Synthesis)，T.W.Greene以及P.G.M.Wuts，第三版，约翰威利国际出版公司(John Wiley&Sons)，1999，通过引用结合在此。示例性氧保护基团包括但不限于，甲基、甲氧基甲基(MOM)、甲基硫代甲基(MTM)、(苯基二甲基甲硅烷基)甲氧基甲基(SMOM)、苄基氧甲基(BOM)、对甲氧基苄基氧甲基(PMBM)、(4-甲氧基苯氧基)甲基(p-AOM)、愈创木酚甲基(GUM)、叔丁氧基甲基、4-戊烯基氧甲基(POM)、硅氧基甲基、2-甲氧基乙氧基甲基(MEM)、2-(三甲基硅烷基)乙氧基甲基(SEMOR)、四氢吡喃基(THP)、4-甲氧基四氢吡喃基(MTHP)、1-[(2-氯-4-甲基)苯基]-4-甲氧基哌啶-4-基(CTMP)、1-乙氧基乙基、1-(2-氯乙氧基)乙基、2-三甲基硅烷基乙基、2-(苯基氢硒基)乙基、叔丁基、烯丙基、对氯苯基、对甲氧基苯基、2,4-二硝基苯基、苄基(Bn)、对甲氧基苄基、3,4-二甲氧基苄基、邻硝基苄基、对硝基苄基、对卤代苄基、三甲基硅烷基(TMS)、三乙基甲硅烷基(TES)、三异丙基甲硅烷基(TIPS)、二甲基异丙基甲硅烷基(IPDMS)、二乙基异丙基甲硅烷基(DEIPS)、二甲基己基甲硅烷基、叔丁基二甲基甲硅烷基(TBDMS)、叔丁基二苯基甲硅烷基(TBDPS)、三苄基甲硅烷基、三-对二甲苯基甲硅烷基、三苯基甲硅烷基、二苯基甲基甲硅烷基(DPMS)、叔丁基甲氧基苯基甲硅烷基(TBMPS)、甲酸酯、9-芴基甲基碳酸酯(Fmoc)、2-(三甲基硅烷基)乙基碳酸酯(TMSEC)、2-(苯磺酰基)乙基碳酸酯(Psec)、2-(三苯基磷基)乙基碳酸酯(Peoc)、硫酸酯、甲磺酸酯(mesylate)、苄基磺酸酯以及甲苯磺酸酯(Ts)。
本发明中，术语“烷基”是指直链或支链的饱和烃基团。
本发明中，术语“烯基”是指具一个或多个碳碳双键并且没有碳碳三键的直链或支链的烃基团。该一个或多个碳碳双键可以是内部的(例如在2-丁烯基中)或末端的(例如在1-丁烯基中)。
本发明中，术语“炔基”是指一个或多个碳碳三键以及任选地一个或多个碳碳双键的直链或支链的烃基团。
本发明中，术语“环烷基”是指饱和的单环、或者包含稠合的、桥联的或螺的多环系统的碳环取代基。
本发明中，“杂环烷基”是指非芳香族环系统的“杂环烷基”。杂环烷基团或者可以是单环的(“单环的杂环基”)或者是稠合的、桥联的或螺的环系统(例如二环系统(“二环的杂环基”))并且可以是饱和的或可以是部分不饱和的。
本发明中，“杂环烯基”是指含有烯键的、不饱和的非芳香族环系统的“杂环基”。杂环烯基团或者可以是单环的(“单环的杂环烯基”)或者是稠合的、桥联的或螺的环系统(例如二环系统(“二环的杂环烯基”))并且可以是饱和的或可以是部分不饱和的。在一些实施例中，杂环烯基是指杂原子为N、O和S中的一种或多种，杂原子数为1～2个，5～6元的杂环烯基。示例性1,2,5,6-四氢吡啶基、4,5-二氢恶唑基。
本发明中，术语“烷氧基”表示通过氧桥连接的环状或者非环状烷基，烷基和环烷基的定义均如前所述。
本发明中，“芳基”是指具有6-14个原子以及零个杂原子、单环的或多环的(例如，二环的或三环的)4n+2芳香族环系统(例如，在循环阵列中具有6，10，或14个共享的p电子)的基团(“C6-C14芳基”)。
本发明中，“杂芳基”是指具有碳原子以及提供在该芳香族环系统中的1-4个杂原子(其中每个杂原子独立地选自氮、氧以及硫)的5-10元单环的或二环的4n+2芳香族环系统(例如，在循环阵列中具有6或10个共享的p电子)的基团(“5-10元杂芳基”)。在包含一个或多个氮原子的杂芳基基团中，连接点可以是碳或氮原子，只要化合价允许。
在不违背本领域常识的基础上，上述各优选条件，可任意组合，即得本发明各较佳实例。
本发明所用试剂和原料均市售可得。
本发明的积极进步效果在于：本发明的烯丙基腈类化合物的制备方法收率高、底物普适性广、官能团兼容性好、或者对应选择性控制较好，而且还具有反应条件温和和操作简单。
附图说明
图1为实施例2中化合物I’-7的X-射线单晶衍射图。
具体实施方式
下面通过实施例的方式进一步说明本发明，但并不因此将本发明限制在所述的实施例范围之中。下列实施例中未注明具体条件的实验方法，按照常规方法和条件，或按照商品说明书选择。
实施例1 N-氟代-N-烷基苯磺酰胺的制备：
在500mL圆底瓶中加入NaH(3.6g,60mmol,60wt％分散于固体石蜡中)，加入CH2Cl2(250mL)。将烷基苯磺酰胺(7.43g,30mmol)溶于CH2Cl2(50mL)中，于0℃下加入到上述反应液，搅拌反应30分钟后,缓慢加入NFSI(37.3g,120mmol)，反应6小时后倒入冰水中淬灭，加入二氯甲烷(50mL*3)萃取，旋干后经过柱层析(石油醚：乙酸乙酯＝20：1)得到式A-1所示的化合物，白色固体(4.07g,51％yield)。
1H NMR(400MHz,CDCl3)δ7.92(d,J＝8.8Hz,2H),7.54(d,J＝8.4Hz,2H),1.48(d,J＝0.4Hz,9H)；13C NMR(100MHz,CDCl3)δ141.0,135.7,130.4,129.3,66.8(d,J＝12.2Hz),27.1(d,J＝6.1Hz)；19F NMR(376MHz,CDCl3)δ-61.92(s).HRMS:m/z(EI)理论值[M]+:265.0340,检测值:265.0342.IR(neat,cm-1):2981,1573,1368,1192,1088,823,797,753,627,568,499,447.
按上述操作步骤得得到式A-2所示的化合物，白色固体(4.4g,45％yield)。1H NMR(400MHz,CDCl3)δ7.78(d,J＝7.2Hz,2H),7.48-7.45(m,4H),7.33-7.27(m,3H),1.87(s,6H)；13C NMR(100MHz,CDCl3)δ142.4(d,J＝2.2Hz),140.7,135.3,130.2,129.1,128.1,127.7,125.8,69.8(d,J＝12.9Hz),26.4(d,J＝5.9Hz)；19F NMR(376MHz,CDCl3)δ-61.02(s).HRMS:m/z(EI)理论值[M]+:327.0496,检测值:327.0501.IR(neat,cm-1):2989,1581,1360,1189,1112,962,915,829,559,483,441.
按上述操作步骤得得到式A-3所示的化合物，白色固体(4.4g,41％yield)。1H NMR(400MHz,CDCl3)δ7.86(d,J＝8.0Hz,2H),7.65(d,J＝8.0Hz,2H),7.38(d,J＝6.0Hz,2H),7.22-7.17(m,3H),1.81(s,6H)；13C NMR(100MHz,CDCl3)δ142.0(d,J＝4.7Hz),140.3,135.5(q,J＝33.9Hz),129.5,128.3,128.0,126.0(q,J＝3.2Hz),125.9,123.0(q,J＝271.4Hz),70.1(d,J＝12.4Hz),26.7(d,J＝5.6Hz)；19F NMR(376MHz,CDCl3)δ-61.31(s),-63.33(s).HRMS:m/z(ESI)理论值[M+Na]+:384.0657,检测值:384.0648.IR(neat,cm-1)3000,1364,1318,1158,1132,1014,899,765,734,551,422.
按上述操作步骤得得到式A4所示的化合物，白色固体(2.9g,40％yield)。1H NMR(400MHz,CDCl3)δ7.86(d,J＝8.4Hz,2H),7.35(d,J＝8.0Hz,2H),2.45(s,3H),1.45(d,J＝2.0Hz,9H)；13C NMR(100MHz,CDCl3):δ145.4,134.3,129.6,129.1,66.4(d,J＝12.6Hz),27.2(d,J＝6.0Hz).19F NMR(375MHz,CDCl3)δ-62.55.HRMS:m/z(EI)理论值[M]+:245.0886,检测值:245.0894.
按上述操作步骤得得到式A5所示的化合物，白色固体(2.8g,36％yield)。1H NMR(400MHz,CDCl3)δ7.92-7.88(m,2H),7.02-6.99(m,2H),3.88(s,3H),1.45(d,J＝1.6Hz,9H)；13C NMR(100MHz,CDCl3):δ164.2,131.3,128.6,114.2,66.3(d,J＝11.6Hz),27.1(d,J＝6.0Hz).19F NMR(375MHz,CDCl3)δ-62.40.HRMS:m/z(EI)理论值[M]+:261.0835,检测值:261.0822.
按上述操作步骤得得到式A6所示的化合物，白色固体(3.3g,38％yield)。1H NMR(400MHz,CDCl3)δ7.90(d,J＝8.8Hz,2H),7.56(d,J＝8.8Hz,2H),1.47(d,J＝1.6Hz,9H),1.35(s,9H)；13C NMR(100MHz,CDCl3):δ158.3,134.2,128.9,126.0,66.4,35.3,31.0,27.2(d,J＝6.0Hz).19F NMR(375MHz,CDCl3)δ-62.46.HRMS:m/z(EI)理论值[M]+:287.1355,检测值:287.1356.
按上述操作步骤得得到式A7所示的化合物，白色固体(3.6g,39％yield)。1H NMR(400MHz,CDCl3)δ8.04(d,J＝8.4Hz,2H),7.76-7.74(m,2H),7.62-7.60(m,2H),7.50-7.41(m,3H),1.50(s,9H)；13C NMR(100MHz,CDCl3):δ147.2,139.0,135.8,129.6,129.1,128.7,127.6,127.4,66.6(d,J＝11.8Hz),27.2(d,J＝6.0Hz).19F NMR(375MHz,CDCl3)δ-62.22.HRMS:m/z(EI)理论值[M]+:307.1042,检测值:307.1045.
按上述操作步骤得得到式A8所示的化合物，黄色液体(2.7g,37％yield)。1H NMR(400MHz,CDCl3)δ8.02-7.98(m,2H)7.27-7.21(m,2H),1.48(d,J＝2.0Hz,9H)；13C NMR(100MHz,CDCl3):δ166.1(d,J＝256.0Hz),133.3(d,J＝2.8Hz),132.0(d,J＝9.7Hz),116.3(d,J＝23.7Hz),66.7(d,J＝11.8Hz),27.2(d,J＝6.1Hz).19F NMR(375MHz,CDCl3)δ-61.93,-102.42HRMS:m/z(EI)理论值[M]+:249.0635,检测值:249.0641.
按上述操作步骤得得到式A9所示的化合物，黄色液体(2.7g,37％yield)。1H NMR(400MHz,CDCl3)δ7.97-7.93(m,1H),7.70-7.65(m,1H),7.34-7.22(m,2H),1.53(d,J＝1.6Hz,9H)；13C NMR(100MHz,CDCl3):δ159.7(d,J＝260.3Hz),136.8(d,J＝9.1Hz),131.9,125.1(d,J＝12.4Hz),124.3(d,J＝3.7Hz),117.5(d,J＝21.4Hz)66.6(d,J＝12.9Hz),27.2(d,J＝6.7Hz).19F NMR(375MHz,CDCl3)δ-61.48,-105.60.HRMS:m/z(EI)理论值[M]+:249.0635,检测值:249.0637.
按上述操作步骤得得到式A10所示的化合物，黄色液体(4.0g,50％yield)。1H NMR(400MHz,CDCl3)δ8.14(d,J＝8.4Hz,1H),7.60-7.55(m,2H),7.46-7.42(m,1H),1.56(s,9H)；13C NMR(100MHz,CDCl3):δ135.1,134.5,133.8,132.9,132.3,126.9,67.2(d,J＝11.9Hz),27.2(d,J＝6.9Hz).19F NMR(375MHz,CDCl3)δ-61.00.HRMS:m/z(EI)理论值[M]+:265.0340,检测值:265.0342.
按上述操作步骤得得到式A11所示的化合物，白色固体(3.4g,40％yield)。1H NMR(400MHz,CDCl3)δ8.55(s,1H),7.99-7.90(m,4H),7.69-7.60(m,2H),1.45(d,J＝0.8Hz,9H)；13C NMR(100MHz,CDCl3):δ135.5,134.1,131.9,131.1,129.5,129.2,127.9,127.6,127.4,66.6(d,J＝11.8Hz),27.2(d,J＝6.0Hz).19F NMR(375MHz,CDCl3)δ-62.09.HRMS:m/z(EI)理论值[M]+:281.0886,检测值:281.0880.
按上述操作步骤得得到式A12所示的化合物，白色固体(3.0g,37％yield)。1H NMR(400MHz,CDCl3)δ8.12(d,J＝8.0Hz,2H),7.84(d,J＝8.0Hz,2H),1.51(s,9H)；13C NMR(100MHz,CDCl3):δ140.8,135.6,129.6,126.1,123.0(d,J＝271.4Hz),67.1(d,J＝12.0Hz),27.2(d,J＝5.8Hz).19F NMR(375MHz,CDCl3)δ-61.77,-63.33.HRMS:m/z(EI)理论值[M]+:299.0603,检测值:299.0615.
实施例2烯丙基氰类化合物的制备
通用操作步骤1：在10mL反应管内，双噁唑啉配体(5.6mg,0.015mmol,7.5mol％)和CuOAc(1.2mg,0.01mmol,5mol％)在氩气保护下，溶解于C6F6(1.0mL)中，室温搅拌，反应液成棕褐色。0.5小时后，依次向反应管内加入式A-3化合物(0.60mmol,3.0equiv),TMSCN(0.60mmol,3.0equiv)和式I所示的多取代烯烃(0.20mmol,1.0equiv)。反应溶液由棕褐色变成蓝色。反应在室温下搅拌反应24小时。反应结束后，减压除去体系中的溶剂六氟苯，残留物用20mL乙酸乙酯稀释，水洗(10mL×3)。有机相经无水MgSO4干燥，过滤，滤液经浓缩后，快速柱层析分离(石油醚/乙酸乙酯)得到目标产物。
通用操作步骤2：在10mL反应管内，双噁唑啉配体(5.6mg,0.015mmol,7.5mol％)和CuOAc(1.2mg,0.01mmol,5mol％)在氩气保护下，溶解于C6F6(1.0mL)中，室温搅拌，反应液成棕褐色。0.5小时后，依次向反应管内加入式A化合物(0.60mmol,3.0equiv),TMSCN(0.60mmol,3.0equiv)和式I所示的多取代烯烃(0.20mmol,1.0equiv)。反应溶液由棕褐色变成蓝色。反应在0℃下搅拌反应36小时。反应结束后，减压除去体系中的溶剂六氟苯，残留物用20mL乙酸乙酯稀释，水洗(10mL×3)。有机相经无水MgSO4干燥，过滤，滤液经浓缩后，快速柱层析分离(石油醚/乙酸乙酯)得到目标产物。
化合物I’-1：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物27.4mg，收率80％。
[α]D 29.9-9.39(c 1.00,CHCl3,92％ee).1H NMR(400MHz,CDCl3)δ7.39-7.25(m,5H),6.73(d,J＝15.6Hz,1H),6.03(dd,J＝16.0Hz,J＝6.4Hz,1H),3.38(q,J＝6.8Hz,1H),1.86-1.77(m,2H),1.12(t,J＝7.6Hz,3H)；13C NMR(100MHz,CDCl3)δ135.7,133.3,128.6,128.2,126.5,122.9,120.0,35.8,26.6,11.2.HRMS:m/z(EI)理论值[M]+:171.1048,检测值:171.1046.IR(neat,cm-1):2926,2859,2241,1455,966,745,693.HPLC(AY-3,0.46*25cm,5μm,hexane/isopropanol＝93/7,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝7.15min(minor)and 7.56min(major).
化合物I’-2：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物35.9mg，收率79％。
[α]D 29.9-5.34(c 1.00,CHCl3,92％ee).1H NMR(400MHz,CDCl3)δ7.39-7.26(m,5H),6.72(d,J＝16.4Hz,1H),6.04(dd,J＝15.6,6.8Hz,1H),3.42(q,J＝6.8Hz,1H),1.80-1.74(m,2H),1.57-1.50(m,2H),,1.37-1.31(m,6H),0.89(t,J＝6.4Hz,3H)；13C NMR(100MHz,CDCl3):δ135.8,133.1,128.7,128.2,126.5,123.3,120.2,34.4,33.3,31.5,28.7,26.8,22.5,14.0.HRMS:m/z(EI)理论值[M]+:227.1674检测值：227.1680.IR(neat,cm-1):2926,2859,2241,1455,966,745,693.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝93/7,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝5.51min(minor)and5.73min(major).
化合物I’-3：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物32.1mg，收率71％。
[α]D 25.9-11.57(c 0.66,CHCl3,92％ee).1H NMR(400MHz,CDCl3)δ7.39-7.29(m,5H),6.75(d,J＝16.0Hz,1H),6.03(dd,J＝16.0,6.4Hz,1H),3.49-3.48(m,1H),3.40-3.37(m,2H),1.90-1.80(m,4H)；13C NMR(100MHz,CDCl3):δ135.5,133.8,128.7,128.4,126.5,122.3,119.6,50.7,34.0,30.4,26.1.HRMS:m/z(EI)理论值[M]+:226.1218,检测值:226.1221.IR(neat,cm-1):2932,2093,1450,1254,1166,1060,965,747,694.HPLC(IC,0.46*25cm,5μm,hexane/isopropanol＝9/1,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝16.27min(minor)and 17.63min(major).
化合物I’-4：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物42.7mg，收率83％。
[α]D 25.9-11.57(c 0.66,CHCl3,90％ee).1H NMR(400MHz,CDCl3)δ7.39-7.26(m,5H),6.73(d,J＝16.0Hz,1H),6.03(dd,J＝16.0,6.4Hz,1H),4.09(t,J＝6.0Hz,2H),3.45(q,J＝7.2Hz,1H),2.05(s,3H),1.84-1.55(m,6H)；13C NMR(100MHz,CDCl3)δ171.1,135.5,133.4,128.7,128.3,126.5,122.7,119.9,63.8,34.3,32.8,28.0,23.3,20.9.HRMS:m/z(EI)理论值[M]+:257.1416,检测值:257.1424.IR(neat,cm-1):2938,1730,1454,1368,1235,1035,753,699.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝93/7,flow0.7mL/min,detection at 214nm)保留时间(retention time)＝6.91min(major)and7.76min(minor).
化合物I’-5：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物27.5mg，收率60％。
[α]D 29.4-2.10(c 1.00,CHCl3,89％ee).1H NMR(400MHz,CDCl3)δ7.39-7.27(m,5H),6.48(d,J＝16.0Hz,1H),6.03(dd,J＝16.0,6.4Hz,1H),3.69(s,3H),3.61(q,J＝7.6Hz,1H),2.57(t,J＝6.8Hz,2H),2.16-2.08(m,2H)；13C NMR(100MHz,CDCl3):δ172.6,135.4,134.0,128.7,128.4,126.6,122.0,119.4,51.9,33.5,30.6,28.1.HRMS:m/z(EI)理论值[M]+:229.1103,检测值:229.1106.IR(neat,cm-1):2949,1730,1441,1164,970,896,748,695.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝8/2,flow 0.7mL/min,detectionat 214nm)保留时间(retention time)＝4.51min(minor)and 4.80min(major).
化合物I’-6：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物29.4mg，收率67％。
[α]D 29.4-8.07(c 1.00,CHCl3,92％ee).1H NMR(400MHz,CDCl3)δ7.39-7.25(m,5H),6.74(d,J＝16.0Hz,1H),6.03(dd,J＝16.0,6.4Hz,1H),3.61-3.58(m,2H),3.49-3.48(m,1H),1.01-1.92(m,4H)；13C NMR(100MHz,CDCl3)δ135.4,133.7,128.7,128.3,126.5,122.3,119.6,43.9,33.7,30.3,29.3.HRMS:m/z(EI)理论值[M]+:219.0815,检测值:219.0812.IR(neat,cm-1):2954,1729,1494,1448,1303,1075,967,897,746,695,649.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝93/7,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝10.45min(major)and 11.77min(minor).
化合物I’-7：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到固体产物57.5mg，收率65％。
[α]D 29.4-72.65(c 1.00,CHCl3,94％ee).1H NMR(400MHz,CDCl3)δ7.85-7.81(m,2H),7.73-7.70(m,2H),7.62(d,J＝8.4Hz,2H),7.07(d,J＝8.0Hz,2H),6.69(d,J＝16.0Hz,1H),6.08(dd,J＝16.0,6.4Hz,1H),3.91-3.87(m,2H),3.52-3.50(m,1H),2.27-2.14(m,2H)；13C NMR(100MHz,CDCl3)δ168.1,137.7,134.8,134.1,133.1,131.7,128.2,123.4,122.5,119.0,93.9,35.1,32.1,31.5.HRMS:m/z(EI)理论值[M]+:442.0178,检测值:442.0182.IR(neat,cm-1):1765,1702,1432,1386,1349,1178,1108,1005,959,891,848,795,712.HPLC(IC,0.46*25cm,5μm,hexane/isopropanol＝7/3,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝31.68min(minor)and 38.11min(major).
式I’-7所示的化合物的单晶制备
将保留时间为38.11min的产物进行单晶培养。将保留时间为38.11min的产物在二氯甲烷中溶解，室温下挥发溶剂，获得无色晶体。
检测方法X-射线单晶衍射
经检测，式I’-7所示的化合物的晶系属于单斜晶系，P21空间群，晶胞参数为
α＝γ＝90°,β＝91.5420(10)°；其单晶参数如下表所示；其X-射线单晶衍射如图1所示。
由所得X-射线单晶衍射的表征结果表明，可以确定化合物I’-7的构型为
从而推导出在配体
存在下，得到的主要产物的构型为R型。
根据本领域中将手性配体用于该类反应中，可以得知，在该配体的对映体
存在下，得到与构型相反的产物。
化合物I’-8：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物36.2mg，收率88％。
[α]D 29.4-4.11(c 1.00,CHCl3,91％ee).1H NMR(400MHz,CDCl3)δ7.38-7.26(m,4H),6.68(d,J＝16.0Hz,1H),6.01(ddd,J＝16.0,6.4,1.6Hz,1H),3.41-3.36(m,1H),1.86-1.77(m,2H),1.14-1.10(m,3H)；13C NMR(100MHz,CDCl3):δ134.2,133.8,132.0,128.8,127.7,123.6,119.8,35.8,26.5,11.1.HRMS:m/z(EI)理论值[M]+:205.0658检测值:205.0661.IR(neat,cm-1):2973,2859,2241,1455,966,745,676,642.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝93/7,flow 0.7mL/min,detection at 214nm)保留时间(retentiontime)＝9.03min(major)and 12.56min(minor).
化合物I’-9：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物33.0mg，收率72％。
[α]D 29.3 0.69(c 1.00,CHCl3,91％ee).1H NMR(400MHz,CDCl3)δ7.38(d,J＝6.8Hz,2H),7.07(d,J＝6.8Hz,2H),6.71(d,J＝15.6Hz,1H),5.99(dd,J＝16.0,6.0Hz,1H),3.39(q,J＝5.6Hz,1H),2.30(s,3H),1.84-1.79(m,2H),1.12(t,J＝7.2Hz,3H)；13C NMR(100MHz,CDCl3)δ169.4,150.4,133.5,132.3,127.5,123.2,121.8,119.9,35.8,26.6,21.1,11.1.HRMS:m/z(EI)理论值[M]+:229.1103,检测值:229.1104.IR(neat,cm-1):3266,2969,1759,1577,1470,1426,1383,1308,1203,1137,1088,996,869,829,753,708.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝93/7,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝7.74min(minor)and 12.80min(major).
化合物I’-10：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物24.9mg，收率52％。
[α]D 29.3-6.35(c 1.00,CHCl3,90％ee).1H NMR(400MHz,CDCl3)δ7.59(d,J＝8.0Hz,2H),7.48(d,J＝8.0Hz,2H),6.78(d,J＝16.4Hz,1H),6.14(dd,J＝16.0,6.4Hz,1H),3.43(q,J＝6.8Hz,1H),1.89-1.78(m,2H),1.14(t,J＝7.2Hz,3H)；13C NMR(100MHz,CDCl3):δ139.1,132.0,130.0(q,J＝32.8Hz),129.5,126.7,125.7,124.0(q,J＝270.8Hz),119.6,35.8,26.5,11.2.19F NMR(376MHz,CDCl3)δ-63.39(s).HRMS:m/z(EI)理论值[M]+:239.0922,检测值:239.0927.IR(neat,cm-1):2973,1612,1459,1415,1321,1156,1110,1061,1011,969,837,688.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝93/7,flow0.7mL/min,detection at 214nm)保留时间(retention time)＝5.27min(major)and5.88min(minor).
化合物I’-11：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物40.7mg，收率75％。
[α]D 29.2-3.53(c 1.00,CHCl3,90％ee).1H NMR(400MHz,CDCl3)δ7.62(d,J＝8.0Hz,2H),7.42(d,J＝8.0Hz,2H),6.75(d,J＝16.0Hz,1H),6.13(dd,J＝16.0,6.4Hz,1H),3.45-3.40(m,1H),1.88-1.79(m,2H),1.13(t,J＝7.2Hz,3H)；13C NMR(100MHz,CDCl3)δ138.3,136.6,132.0,129.4(q,J＝306.2Hz),127.4,125.5,123.8,119.6,35.8,26.5,11.2.19F NMR(376MHz,CDCl3)δ-42.21(s).HRMS:m/z(EI)理论值[M]+:271.0643,检测值:271.0644.IR(neat,cm-1):2980,1459,1399,1113,962,813,757.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝93/7,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝15.04min(major)and 17.63min(minor).
化合物I’-12：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物31.1mg，收率69％。
[α]D 25.9-11.57(c 0.66,CHCl3,89％ee).1H NMR(400MHz,CDCl3)δ7.38-7.12(m,4H),6.73(d,J＝15.6Hz,1H),6.08(dd,J＝16.0,6.4Hz,1H),3.41(q,J＝6.4Hz,1H),1.88-1.77(m,2H),1.13(t,J＝7.2Hz,3H)；13C NMR(100MHz,CDCl3):δ149.5,137.8,131.9,130.0,124.9,124.8,120.4(q,J＝255.9Hz),120.4,119.6,118.7,35.8,26.5,11.1.19F NMR(376MHz,CDCl3)δ-57.80(s).HRMS:m/z(EI)理论值[M]+:255.0871,检测值:255.0875.IR(neat,cm-1):2932,2859,2241,1455,966,745,683.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝93/7,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝4.88min(minor)and 6.75min(major).
化合物I’-13：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到固体产物33.2mg，收率70％。
[α]D 29.2-0.82(c 1.00,CHCl3,90％ee).1H NMR(400MHz,CDCl3)δ7.94(d,J＝2.8Hz,1H),7.73(d,J＝1.6Hz,1H),7.69-7.67(m,2H),7.48-7.46(m,2H),6.75(d,J＝16.0Hz,1H),6.48(t,J＝2.0Hz,1H),6.05(dd,J＝16.0,6.8Hz,1H),3.42-3.40(m,1H),1.87-1.82(m,2H),1.14(t,J＝7.2Hz,3H)；13C NMR(100MHz,CDCl3)δ141.3,139.8,133.9,132.3,127.6,126.6,123.2,119.9,119.2,107.8,35.9,26.6,11.3.HRMS:m/z(EI)理论值[M]+:237.1266,检测值:237.1273.IR(neat,cm-1):3111,2974,1600,1516,1385,1329,1253,1199,1121,1025,932,838,763.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝7/3,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝12.13min(major)and 14.38min(minor).
化合物I’-14：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物28.7mg，收率81％。
[α]D 28.8-17.43(c 1.00,CHCl3,92％ee).1H NMR(400MHz,CDCl3)δ7.30-7.28(m,1H),7.20-7.18(m,2H),6.73(d,J＝15.6Hz,1H),5.89(dd,J＝15.6,6.0Hz,1H),3.35(q,J＝7.2Hz,1H),1.84-1.74(m,2H),1.13-1.09(m,3H)；13C NMR(100MHz,CDCl3)δ138.2,127.4,126.3,124.6,123.1,122.7,120.0,35.7,26.5,11.1.HRMS:m/z(EI)理论值[M]+:177.0612,检测值:177.0616.IR(neat,cm-1):2969,2240,1456,1246,1159,1084,962,828,772,694.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝93/7,flow 0.7mL/min,detectionat 214nm)保留时间(retention time)＝16.52min(major)and 22.15min(minor).
化合物I’-15：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物26.6mg，收率52％。
[α]D25.9-11.57(c 0.66,CHCl3,90％ee).1H NMR(400MHz,CDCl3)δ7.09(s,1H),6.92(s,1H),6.78(d,J＝16.0Hz,1H),5.89(dd,J＝16.0,6.4Hz,1H),3.37(q,J＝6.0Hz,1H),1.85-1.76(m,2H),1.14(t,J＝7.2Hz,3H)；13C NMR(100MHz,CDCl3)δ141.3,128.6,125.3,123.7,121.9,119.4,110.2,35.6,26.5,11.2.HRMS:m/z(EI)理论值[M]+:254.9717,检测值:254.9719.IR(neat,cm-1):2970,2934,2876,2338,2242,1667,1512,1459,1385,1336,1279,1251,1223,1167,1120,1077,954,870,822,737,667,662,585.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝93/7,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝10.65min(major)and 12.03min(minor).
化合物I’-16：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物20.3mg，收率63％。
[α]D 29.0-27.00(c 1.00,CHCl3,93％ee).1H NMR(400MHz,CDCl3)δ7.46(s,1H),7.39(s,1H),6.60(d,J＝15.6Hz,1H),6.51(s,1H),5.76(dd,J＝15.6,6.4Hz,1H),3.34(q,J＝6.8Hz,1H),1.83-1.75(m,2H),1.11(t,J＝7.2Hz,3H)；13C NMR(100MHz,CDCl3)δ143.8,141.1,123.1,122.8,122.4,120.0,107.2,35.8,26.6,11.2.HRMS:m/z(EI)理论值[M]+:161.0841,检测值:161.0839.IR(neat,cm-1):2971,2936,2879,2242,1750,1460,1384,1344,1259,1083,1051,971,815,600.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝99/1,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝13.39min(major)and 16.27min(minor).
化合物I’-17：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物42.1mg，收率88％。
[α]D 28.6-50.69(c 1.00,CHCl3,94％ee).1H NMR(400MHz,CDCl3)δ8.02(s,1H),7.88-7.83(m,3H),7.54-7.51(m,3H),5.51(dd,J＝33.6,9.2Hz,1H),3.83-3.77(m,1H),1.93-1.81(m,2H),1.16(t,J＝7.6Hz,3H)；13C NMR(100MHz,CDCl3)δ159.1(d,J＝253.2Hz),137.7,132.8,128.6,128.5(d,J＝3.3Hz),128.0,127.7,127.2,126.9,124.2(d,J＝6.6Hz),121.5(d,J＝6.9Hz),120.2,100.7(d,J＝15.8Hz),28.4(d,J＝6.8Hz),26.8,11.4.19F NMR(376MHz,CDCl3)δ-114.12(d,J＝33.4Hz).HRMS:m/z(EI)理论值[M]+:239.1110,检测值:239.1118.IR(neat,cm-1):2973,1672,1456,1357,1300,1191,1132,1008,934,870,816,750.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝93/7,flow0.7mL/min,detection at 214nm)保留时间(retention time)＝7.60min(minor)and12.78min(major).
化合物I’-18：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物26.0mg，收率52％。
[α]D 28.5-21.96(c 1.00,CHCl3,85％ee).1H NMR(400MHz,CDCl3)δ7.53-7.52(m,2H),7.37-7.36(m,3H),6.16(d,J＝8.8Hz,1H),3.78(q,J＝7.6Hz,1H),1.92-1.83(m,2H),1.17(t,J＝7.2Hz,3H)；13C NMR(100MHz,CDCl3)δ138.4,130.1,129.5,128.5,127.7,124.7,119.5,35.9,25.4,11.4.HRMS:m/z(EI)理论值[M]+:249.0153,检测值:249.0160.IR(neat,cm-1):2970,2241,1686,1630,1450,1384,1229,1076,897,840,757,691,647.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝9/1,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝10.83min(major)and 11.45min(minor).
化合物I’-19：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物22.9mg，收率50％。
[α]D 28.3-50.71(c 1.00,CHCl3,88％ee).1H NMR(400MHz,CDCl3)δ7.41-7.35(m,5H),5.65(d,J＝8.8Hz,1H),3.42(q,J＝7.2Hz,1H),2.32(s,3H),1.86-1.78(m,2H),1.13(t,J＝7.6Hz,3H)；13C NMR(100MHz,CDCl3)δ168.2,149.7,133.8,129.3,128.7,124.9,119.7,111.3,29.9,26.4,20.7,11.4.HRMS:m/z(EI)理论值[M]+:229.1103,检测值:229.1106.IR(neat,cm-1):2931,1761,1665,1450,1371,1189,1028,907,756,691.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝93/7,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝14.20min(minor)and 16.01min(major).
化合物I’-20：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物26.7mg，收率54％。
[α]D 26.9-41.76(c 1.00,CHCl3,88％ee).1H NMR(400MHz,CDCl3)δ7.44-7.36(m,3H),7.30-7.19(m,7H),5.96(d,J＝10.0Hz,1H),3.24(dt,J＝10.0,6.8Hz,1H),1.83-1.70(m,2H),1.03(t,J＝7.6Hz,3H)；13C NMR(100MHz,CDCl3)δ146.3,140.7,138.3,129.3,128.7,128.3,128.1,128.0,127.4,122.1,120.8,32.9,27.0,11.3.HRMS:m/z(EI)理论值[M]+:247.1361,检测值:247.1367.IR(neat,cm-1):2969,2236,1590,1504,1455,1374,963,901,964,812,747.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝93/7,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝5.56min(major)and 6.02min(minor).
化合物I’-21：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物22.0mg，收率48％。
[α]D 28.3-4.22(c 1.00,CHCl3,93％ee).1H NMR(400MHz,CDCl3)δ7.39-7.26(m,5H),6.41(s,1H),3.65-3.62(m,1H),2.22(s,3H),1.95-1.85(m,2H),1.16(t,J＝7.2Hz,3H)；13CNMR(100MHz,CDCl3)δ168.1,141.9,132.9,128.6,128.4,128.1,119.2,118.4,37.9,24.2,20.9,11.1.HRMS:m/z(EI)理论值[M]+:229.1103,检测值:229.1106.IR(neat,cm-1):2956,2922,2853,1764,1494,1461,1373,1258,11993,1143,1091,1011,793,752,695.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝93/7,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝10.42min(major)and 14.15min(minor).
化合物I’-22：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物29.2mg，收率60％。
[α]D 26.5-25.03(c 0.60,CHCl3,86％ee).1H NMR(400MHz,CDCl3)δ7.51-7.48(m,2H),7.37-7.36(m,3H),6.21(d,J＝18.4Hz,1H),5.87(dd,J＝18.4,5.6Hz,1H),3.32(q,J＝6.4Hz,1H),1.67-1.43(m,4H),0.96(t,J＝7.6Hz,3H),0.36(s,6H)；13C NMR(100MHz,CDCl3)δ140.1,137.5,133.8,132.3,129.2,127.9,120.1,37.4,34.6,20.1,13.5,-2.7,-2.8.HRMS:m/z(EI)理论值[M]+:243.1443,检测值:243.1444.IR(neat,cm-1):2957,1614,1424,1252,1110,989,826,732,697.HPLC(IG,0.46*25cm,5μm,hexane/isopropanol＝99/1,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝8.26min(minor)and 8.80min(major).
化合物I’-23：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物34.1mg，收率70％。
[α]D 26.4-10.78(c 0.50,CHCl3,90％ee).1H NMR(400MHz,CDCl3)δ7.91-7.89(m,2H),7.79-7.77(m,2H),6.99(d,J＝14.8Hz,1H),6.63(dd,J＝14.8,7.2Hz,1H),3.34(q,J＝6.8Hz,1H),1.88-1.81(m,2H),1.13(t,J＝7.6Hz,3H)；13C NMR(100MHz,CDCl3)δ166.1,134.7,131.4,123.8,120.9,119.5,114.4,34.5,26.8,11.2.HRMS:m/z(EI)理论值[M]+:240.0899,检测值:240.0910.IR(neat,cm-1):2930,1771,1711,1462,1376,1086,969,875,798,710.HPLC(IC,0.46*25cm,5μm,hexane/isopropanol＝5/5,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝22.25min(major)and 30.28min(minor).
化合物I’-24：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物41.5mg，收率88％。
[α]D 26.8-69.42(c 1.00,CHCl3,97％ee).1H NMR(400MHz,CDCl3)δ7.45-7.37(m,4H),3.83(t,J＝6.0Hz,1H),2.71-2.51(m,2H),2.16-1.89(m,3H),1.87-1.84(m,1H)；13CNMR(100MHz,CDCl3)δ151.9(d,J＝243.4Hz),134.9,130.2(d,J＝28.3Hz),128.6(d,J＝1.1Hz),127.5(d,J＝6.6Hz),120.2(d,J＝2.4Hz),117.3(d,J＝19.1Hz),31.5,31.0(d,J＝3.7Hz),29.7(d,J＝2.7Hz),26.4.19F NMR(376MHz,CDCl3)δ-102.89(s).HRMS:m/z(EI)理论值[M]+:235.0564,检测值:235.0573.IR(neat,cm-1):2938,2237,1673,1590,1485,1399,1256,1167,1082,1006,832,636.HPLC(IC,0.46*25cm,5μm,hexane/isopropanol＝9/1,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝21.10min(minor)and 23.71min(major).
化合物I’-25：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物39.6mg，收率75％。
[α]D 26.5-265.84(c 1.00,CHCl3,95％ee).1H NMR(400MHz,CDCl3)δ7.40-7.35(m,4H),4.17-4.13(m,1H),2.42-2.38(m,2H),2.04-1.99(m,2H),1.89-1.84(m,2H),1.65-1.53(m,4H)；13C NMR(100MHz,CDCl3)δ154.3(d,J＝246.6Hz),135.4(d,J＝1.6Hz),129.9,129.5(d,J＝4.9Hz),128.6,120.4(d,J＝1.6Hz),115.4(d,J＝13.4Hz),30.9,29.8(d,J＝9.8Hz),28.3,27.9(d,J＝2.6Hz),27.2(d,J＝2.4Hz),26.5.19F NMR(376MHz,CDCl3)δ-97.40(s).HRMS:m/z(EI)理论值[M]+:263.0877检测值:263.0884.IR(neat,cm-1):2928,2857,1665,1592,1481,1451,1397,1257,1148,1089,1048,1007,883,826,766,725,631.HPLC(IC,0.46*25cm,5μm,hexane/isopropanol＝9/1,flow 0.7mL/min,detection at214nm)保留时间(retention time)＝16.99min(major)and 17.83min(minor).
化合物I’-26：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物38.5mg，收率66％。
[α]D 26.3 12.67(c 0.60,CHCl3,82％ee).1H NMR(400MHz,CDCl3)δ7.80(d,J＝8.4Hz,2H),7.80(d,J＝8.0Hz,2H),5.40(d,J＝7.2Hz,1H),3.36-3.33(m,1H),2.52-2.32(m,5H),1.97-1.52(m,6H)；13C NMR(100MHz,CDCl3)δ155.8,145.5,132.5,129.9,128.4,119.2,116.6,32.9,29.8,27.4,27.3,23.9,21.7.HRMS:m/z(ESI)理论值[M+Na]+:314.0821,检测值:314.0818.IR(neat,cm-1):2930,2860,2239,1677,1597,1494,1446,1368,1293,1259,1213,1199,1177,1092,1056,1011,923,814,753,691,664,591,551.HPLC(IC-3,0.46*15cm,3μm,hexane/isopropanol＝8/2,flow 0.7mL/min,detection at214nm)保留时间(retention time)＝37.81min(minor)and 43.17min(major).
化合物I’-27：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物33.9mg，收率51％。
[α]D 27.7-130.87(c 0.20,CHCl3,80％de).1H NMR(400MHz,CDCl3)δ7.70(d,J＝8.0Hz,2H),7.32(d,J＝7.6Hz,2H),5.75(dd,J＝15.2,6.0Hz,1H),5.61(dd,J＝15.2,6.0Hz,1H),4.21-4.18(m,1H),3.45-3.42(m,1H),3.41-3.22(m,2H),2.44(s,3H),1.84-1.41(m,8H),0.97(t,J＝7.6Hz,3H)；13C NMR(100MHz,CDCl3)δ143.5,135.1,134.1,129.7,127.4,125.4,120.2,60.6,48.7,34.9,33.4,32.4,23.8,21.5,20.0,13.5.HRMS:m/z(EI)理论值[M]+:332.1559,检测值:332.1554.IR(neat,cm-1):2960,2931,2874,1727,1597,1455,1342,1196,1156,1092,969,816,664,586,549.HPLC(ID-3,0.46*15cm,3μm,hexane/isopropanol＝8/2,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝20.21min(major)and 21.51min(minor).
化合物I’-28：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物21.9mg，收率52％。
[α]D 29.0-2.70(c 1.00,CHCl3,88％ee).1H NMR(400MHz,CDCl3)δ7.54(d,J＝7.6Hz,1H),7.43(d,J＝8.0Hz,1H),7.31-7.19(m,2H),6.70(d,J＝15.6Hz,1H),6.64(s,1H),6.29(dd,J＝15.6,6.0Hz,1H),3.46-3.44(m,1H),1.88-1.80(m,2H),1.14(t,J＝6.8Hz,3H)；13CNMR(100MHz,CDCl3):δ154.8,152.9,128.6,125.0,124.6,123.0,121.6,121.1,119.5,110.9,105.9,35.7,26.5,11.2.HRMS:m/z(EI)理论值[M]+:211.0997,检测值:211.0996.IR(neat,cm-1):2967,1667,1446,1316,1146,1079,952,817,746.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝93/7,flow 0.7mL/min,detection at 214nm)保留时间(retentiontime)＝8.13min(major)and 9.15min(minor).
化合物I’-29：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物31.8mg，收率70％。
[α]D 29.0-2.70(c 1.00,CHCl3,89％ee).1H NMR(400MHz,CDCl3)δ7.90-7.85(m,2H),7.44-7.36(m,3H),6.99(d,J＝16.0Hz,1H),6.11(dd,J＝15.6,6.0Hz,1H),3.44(q,J＝7.2Hz,1H),1.90-1.82(m,2H),1.15(t,J＝7.2Hz,3H)；13C NMR(100MHz,CDCl3):δ140.3,137.3,132.4,125.7,124.7,124.6,124.4,123.0,122.9,121.8,119.9,36.1,26.6,11.2.HRMS:m/z(EI)理论值[M]+:227.0769,检测值:227.0762.IR(neat,cm-1):2976,1681,1447,1311,1145,1077,951,818,746,652.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝93/7,flow0.7mL/min,detection at 214nm)保留时间(retention time)＝6.15min(minor)and 7.18min(major).
化合物I’-30：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物20.6mg，收率51％。
[α]D 29.8-1.40(c 1.00,CHCl3,92％ee).1H NMR(400MHz,CDCl3)δ8.12(s,1H),7.66-7.64(m,1H),6.73(d,J＝8.8Hz,1H),6.66(d,J＝16.0Hz,1H),5.93(dd,J＝15.6,6.4Hz,1H),3.94(s,3H),3.39(q,J＝7.6Hz,1H),1.86-1.78(m,2H),1.14-1.11(m,3H)；13C NMR(100MHz,CDCl3):δ163.9,145.7,135.5,129.5,124.9,122.1,119.9,111.1,53.5,35.8,26.6,11.2.HRMS:m/z(EI)理论值[M]+:202.1106,检测值:202.1100.IR(neat,cm-1):2971,1600,1491,1383,1282,1148,1089,1019,966,827,754.HPLC(IC-3,0.46*15cm,3μm,hexane/isopropanol＝7/3,flow 0.7mL/min,detection at 214nm)保留时间(retentiontime)＝15.86min(major)and 21.75min(minor).
化合物I’-31：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物22.9mg，收率58％。
[α]D 27.3-29.75(c 1.00,CHCl3,96％ee).1H NMR(400MHz,CDCl3)δ7.35-7.32(m,2H),7.26-7.19(m,3H),6.64(s,1H),3.42-3.39(m,1H),2.67-2.61(m,1H),2.29-2.24(m,1H),2.08-2.03(m,1H),1.97-1.88(m,2H),1.66-1.58(m,3H)；13C NMR(100MHz,CDCl3):δ136.5,135.6,128.8,128.2,126.9,125.6,120.2,37.4,32.3,27.6,26.9,24.2.HRMS:m/z(EI)理论值[M]+197.1204,检测值:197.1198.IR(neat,cm-1):3024,2934,2858,2241,1656,1600,1494,1445,1257,1075,1027,925,738,699,504.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝93/7,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝7.35min(minor)and 7.73min(major).
化合物I’-32：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物28.0mg，收率71％。
[α]D 27.2-1.55(c 1.00,CHCl3,91％ee).1H NMR(400MHz,CDCl3)δ7.35-7.24(m,5H),5.95(d,J＝6.4Hz,1H),3.63-3.58(m,1H),2.82-2.75(m,1H),2.62-2.56(m,1H),2.18-2.11(m,1H),2.01-1.83(m,3H),1.75-1.65(m,2H)；13C NMR(100MHz,CDCl3):δ148.6,143.1,128.3,127.5,125.8,123.5,121.4,32.3,30.7,30.6,29.9,25.7.HRMS:m/z(EI)理论值[M]+:197.1204检测值:197.1201.IR(neat,cm-1):2926,2855,2237,1491,1445,1078,970,836,753,695.HPLC(IC-3,0.46*15cm,3μm,hexane/isopropanol＝9/1,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝12.51min(major)and 13.99min(minor).
化合物I’-33：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝20:1)得到油状液体产物27.2mg，收率64％。
[α]D 28.1-18.96(c 0.50,CHCl3,74％ee).1H NMR(400MHz,CDCl3)δ7.95(d,J＝8.0Hz,2H),7.63-7.59(m,1H),7.49(t,J＝7.6Hz,2H),5.13(dt,J＝8.8,1.2Hz,1H),4.11-4.06(m,1H),4.45(dd,J＝18.0,7.2Hz,1H),3.28(dd,J＝18.0,7.2Hz,1H),1.77(d,J＝1.2Hz,3H),1.75(d,J＝1.2Hz,3H)；13C NMR(100MHz,CDCl3)δ195.0,138.7,135.9,133.8,128.8,128.0,120.9,117.7,41.7,25.5,24.9,18.3.HRMS:m/z(EI)理论值[M]+:213.1154,检测值:213.1150.IR(neat,cm-1):3063,2966,2918,2855,1686,1597,1580,1449,1410,1376,1357,1305,1257,1217,1024,800,753,689.HPLC(OD-H,0.46*25cm,5μm,hexane/isopropanol＝8/2,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝11.14min(minor)and 15.99min(major).
化合物I’-34：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝10:1)得到白色固体产物60.1mg，收率91％。
[α]D 29.5-0.21(c 1.00,CHCl3,90％ee).1H NMR(400MHz,CDCl3)δ7.85-7.83(m,2H),7.73-7.71(m,2H),7.37-7.27(m,5H),6.72(d,J＝16.0Hz,1H),6.02(dd,J＝16.0,6.8Hz,1H),3.76(t,J＝6.8Hz,2H),3.54(q,J＝6.0Hz,1H),1.93-1.81(m,4H)；13C NMR(100MHz,CDCl3)δ168.3,135.4,134.0,133.6,131.8,128.6,128.2,126.5,123.3,122.4,119.6,36.8,33.8,30.3,25.9.HRMS:m/z(EI)理论值[M]+:330.1368,检测值:330.1367.IR(neat,cm-1):1761,1701,1394,1112,1035,967,864,710.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝3/1,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝27.35min(minor)and30.52min(major).
化合物I’-35：
该反应按照通用操作步骤2进行，柱层析分离(石油醚：乙酸乙酯＝10:1)得到油状液体产物22.1mg，收率61％。
[α]D 29.8-23.09(c 1.00,CHCl3,91％ee).1H NMR(400MHz,CDCl3)δ8.39(d,J＝2.8Hz,1H),7.67(dd,J＝8.4,4.8Hz,1H),7.31(d,J＝8.4Hz,1H),6.72(d,J＝16.0Hz,1H),6.11(dd,J＝16.0Hz,6.0Hz,1H),3.46-3.40(m,1H),1.89-1.63(m,2H),1.14(t,J＝7.6Hz,3H)；13C NMR(100MHz,CDCl3):δ150.8,148.0,135.8,130.4,128.5,126.1,124.2,119.3,35.9,26.4,11.1.HRMS:m/z(EI)理论值[M]+:206.0611检测值:206.0617.IR(neat,cm-1):3013,2958,2871,1553,1457,1360,1100,839,693,530.HPLC(IG,0.46*25cm,5μm,hexane/isopropanol＝7/3,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝9.63min(minor)and 10.19min(major).
化合物I’-36：
该反应按照通用操作步骤2进行，柱层析分离(石油醚：乙酸乙酯＝10:1)得到油状液体产物58.7mg，收率75％。
[α]D 27.5-3.37(c 1.00,CHCl3,96％ee).1H NMR(400MHz,CDCl3)δ7.65-7.61(m,6H),7.46-7.36(m,9H),6.16(dd,J＝16.0,2.0Hz,1H),6.02(dd,J＝16.0,1.2Hz,1H),3.38-3.33(m,1H),1.73-1.67(m,2H),1.58-1.48(m,2H),0.97(t,J＝7.2Hz,3H)；13C NMR(100MHz,CDCl3)δ138.2,135.5,133.1,130.0,128.0,118.9,113.4,105.8,91.6,34.6,34.1,20.0,13.4.HRMS:m/z(EI)理论值[M]+:391.756,检测值:391.1751.IR(neat,cm-1):2961,2138,1428,1260,1111,953,801,742,508.HPLC(OD-H,0.46*25cm,5μm,hexane/isopropanol＝99/1,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝7.11min(minor)and 7.68min(major).
化合物I’-37：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝10:1)得到油状液体产物32.0mg，收率42％。
[α]D 26.4-7.24(c 1.00,CHCl3,90％ee).1H NMR(400MHz,CDCl3)δ7.87-7.84(m,2H),7.76-7.72(m,2H),6.36(dd,J＝18.0,5.6Hz,1H),5.83(d,J＝18.0Hz,1H),3.74(t,J＝6.4Hz,2H),3.44(q,J＝6.4Hz,1H),1.96-1.82(m,2H),1.79-1.72(m,2H),1.27(s,12H)；13CNMR(100MHz,CDCl3)δ168.3,144.1,134.1,131.9,123.3,119.0,83.6,36.8,36.1,29.5,26.0,24.8,24.73,24.69.HRMS:m/z(EI)理论值[M]+:379.1944,检测值:379.1952.IR(neat,cm-1):2973,1771,1707,1638,1444,1362,1140,1030,845,800,716.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝93/7,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝7.12min(minor)and 8.68min(major).
化合物I’-38：
该反应按照通用操作步骤2进行，柱层析分离(石油醚：乙酸乙酯＝10:1)得到油状液体产物42.4mg，收率56％。
[α]D 26.4-23.46(c 1.00,CHCl3,87％ee).1H NMR(400MHz,CDCl3)δ7.77(d,J＝8.4Hz,2H),7.32(d,J＝8.0Hz,2H),5.97(dtd,J＝15.6,6.0,1.2Hz,1H),5.66(dd,J＝15.6,6.0Hz,1H),4.46(d,J＝6.0Hz,2H),3.26(q,J＝6.4Hz,1H),2.44(s,3H),1.78-1.73(m,2H),1.35(s,9H),1.08(t,J＝7.6Hz,3H)；13C NMR(100MHz,CDCl3)δ150.5,144.4,136.9,129.3,129.2,128.0,127.7,119.7,84.6,47.3,35.2,27.8,26.2,21.6,11.0.HRMS:m/z(ESI)理论值[M+Na]+:401.1505,检测值:401.1502.IR(neat,cm-1):2973,2935,2879,1727,1598,1354,1285,1257,1153,1088,813,719,672,574,546.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝8/2,flow 0.7mL/min,detection at 254nm)保留时间(retention time)＝20.56min(minor)and 25.27min(major).
化合物I’-39：
该反应按照通用操作步骤2进行，柱层析分离(石油醚：乙酸乙酯＝10:1)得到油状液体产物28.0mg，收率58％。
[α]D 27.5-7.35(c 1.00,CHCl3,92％ee).1H NMR(400MHz,CDCl3)δ7.36-7.32(m,2H),7.26-7.21(m,3H),6.64(s,1H),3.33(t,J＝7.2Hz,1H),2.43-2.38(m,1H),2.20-2.13(m,1H),1.82-1.76(m,2H),1.65-1.44(m,4H),1.34-1.26(m,2H),1.00(t,J＝7.2Hz,3H),0.88(t,J＝7.2Hz,3H)；13C NMR(100MHz,CDCl3)δ137.0,136.8,128.9,128.5,128.3,126.9,120.9,38.0,34.5,30.5,29.5,22.7,20.4,13.7,13.5.HRMS:m/z(EI)理论值[M]+:241.1830,检测值:241.1840.IR(neat,cm-1):2949,2866,1455,1259,1026,865,802,742,694.HPLC(AY3,0.46*15cm,3μm,hexane/isopropanol＝9/1,flow 0.7mL/min,detectionat 214nm)保留时间(retention time)＝6.79min(major)and 7.67min(minor).
化合物I’-40：
该反应按照通用操作步骤2进行，柱层析分离(石油醚：乙酸乙酯＝10:1)得到油状液体产物29.9mg，收率70％。
[α]D 27.9-32.23(c 1.00,CHCl3,85％ee).1H NMR(400MHz,CDCl3)δ7.25-7.27(m,5H),5.50(d,J＝9.2Hz,1H),3.48(dt,J＝8.8,7.2Hz,1H),2.52-2.47(m,2H),1.88-1.71(m,2H),1.43-1.32(m,2H),1.12(t,J＝7.6Hz,3H),0.90(t,J＝7.6Hz,3H)；13C NMR(100MHz,CDCl3)δ145.4,141.5,128.3,127.6,126.5,121.9,120.8,32.3,31.6,27.0,21.4,13.8,11.4.HRMS:m/z(EI)理论值[M]+:213.1517,检测值:213.1522.IR(neat,cm-1):2962,2872,2238,1455,1379,1077,868,761,696.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝96/4,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝4.79min(major)and 5.11min(minor).
化合物I’-41：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝10:1)得到油状液体产物58.4mg，收率72％。
[α]D 25.9-30.80(c 0.50,CHCl3,95％ee).1H NMR(400MHz,CDCl3)δ8.05-8.02(m,2H),7.60-7.55(m,1H),7.49-7.42(m,4H),7.38-7.33(m,3H),5.65(d,J＝9.2Hz,1H),4.47-4.38(m,2H),3.82(q,J＝8.4Hz,1H),2.28-2.22(m,1H),2.13-2.03(m,3H),1.19-1.11(m,4H),0.73(t,J＝7.2Hz,3H),0.37(s,6H)；13C NMR(100MHz,CDCl3)δ166.1,147.3,137.1,133.9,133.2,132.3,129.6,129.5,129.3,128.4,127.8,120.3,61.4,32.4,31.8,30.1,26.7,22.9,13.6,-2.9,-3.0.HRMS:m/z(EI)理论值[M]+:405.2124,检测值:405.2117.IR(neat,cm-1):2959,2360,2168,1722,1271,1111,819,711,422.HPLC(IC,0.46*25cm,5μm,hexane/isopropanol＝9/1,flow 0.7mL/min,detection at 214nm)保留时间(retentiontime)＝8.33min(major)and 11.13min(minor).
化合物I’-42：
该反应按照通用操作步骤2进行，柱层析分离(石油醚：乙酸乙酯＝10:1)得到白色固体产物29.3mg，收率52％。
[α]D 22.8-1.09(c 0.30,CHCl3,89％ee).1H NMR(400MHz,CDCl3)δ7.90-7.88(m,2H),7.78-7.76(m,2H),5.50(d,J＝9.6Hz,1H),3.53-3.47(m,1H),2.58-2.43(m,2H),1.94-1.77(m,2H),1.46-1.33(m,2H),1.72(t,J＝7.6Hz,3H),0.93(t,J＝7.6Hz,3H)；13C NMR(100MHz,CDCl3)δ167.1,135.3,134.4,131.6,125.6,123.7,119.7,31.1,30.9,26.9,20.1,13.6,11.3.HRMS:m/z(ESI)理论值[M+H]+:283.1441,检测值:283.1443.IR(neat,cm-1):2970,1720,1378,1259,428.HPLC(IC-3,0.46*15cm,3μm,hexane/isopropanol＝7/3,flow0.7mL/min,detection at 214nm)保留时间(retention time)＝9.10min(major)and10.00min(minor).
化合物I’-43：
该反应按照通用操作步骤2进行，柱层析分离(石油醚：乙酸乙酯＝10:1)得到油状液体产物34.6mg，收率54％。
[α]D 26.4-52.91(c 0.80,CHCl3,94％ee).1H NMR(400MHz,CDCl3)δ7.84(d,J＝8.0Hz,2H),7.40(d,J＝8.0Hz,2H),5.03(d,J＝9.6Hz,1H),3.38-3.32(m,1H),2.48(s,3H),2.27-2.23(m,2H),1.69-1.53(m,2H),1.45-1.37(m,2H),1.30-1.21(m,2H),1.01(t,J＝7.2Hz,3H),0.85(t,J＝7.2Hz,3H)；13C NMR(100MHz,CDCl3)δ151.8,145.8,133.4,130.2,127.9,119.8,113.8,33.5,29.6,28.4,26.5,21.9,21.8,13.7,11.3.HRMS:m/z(EI)理论值[M]+:321.1399,检测值:321.1398.IR(neat,cm-1):2960,2932,2873,1686,1597,1460,1372,1191,1177,1092,898,815,549.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝7/3,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝5.68min(minor)and 8.08min(major).
化合物I’-44：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝10:1)得到油状液体产物32.5mg，收率60％。
[α]D 21.6-17.69(c 0.70,CHCl3,81％ee).1H NMR(400MHz,CDCl3)δ8.06-8.04(m,2H),7.61-7.56(m,1H),7.48-7.44(m,2H),5.51(d,J＝9.2Hz,1H),4.81-4.74(m,2H),3.41-3.35(m,1H),2.17(t,J＝8.0Hz,2H),1.84-1.65(m,2H),1.58-1.49(m,2H),1.08(t,J＝7.2Hz,3H),0.97(t,J＝7.2Hz,3H)；13C NMR(100MHz,CDCl3)δ166.1,139.6,133.2,129.9,129.6,128.5,122.4,120.5,67.1,30.9,30.8,26.8,21.3,14.1,11.4.HRMS:m/z(ESI)理论值[M+H]+:272.1645,检测值:272.1649.IR(neat,cm-1):2966,1721,1452,1069,712.HPLC(OD-H,0.46*25cm,5μm,hexane/isopropanol＝98/2,flow 0.7mL/min,detection at214nm)保留时间(retention time)＝13.75min(minor)and 15.56min(major).
化合物I’-45：
该反应按照通用操作步骤2进行，柱层析分离(石油醚：乙酸乙酯＝10:1)得到白色固体产物30.8mg，收率52％。
[α]D 21.8-2.59(c 0.70,CHCl3,85％ee).1H NMR(400MHz,CDCl3)δ7.88-7.85(m,2H),7.77-7.73(m,2H),5.29(d,J＝9.2Hz,1H),4.30-4.19(m,2H),3.34-3.28(m,1H),2.10-2.01(m,2H),1.78-1.52(m,4H),1.03(t,J＝7.6Hz,3H),0.97(t,J＝7.6Hz,3H)；13C NMR(100MHz,CDCl3)δ167.9,139.0,134.1,131.9,123.4,1218,120.6,42.3,31.2,30.9,26.8,21.2,14.0,11.3.HRMS:m/z(ESI)理论值[M+H]+:297.1598,检测值:297.1601.IR(neat,cm-1):2965,1772,1425,1394,950,726.HPLC(OD-H,0.46*25cm,5μm,hexane/isopropanol＝98/2,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝31.96min(minor)and 34.20min(major).
化合物I’-46：
该反应按照通用操作步骤2进行，柱层析分离(石油醚：乙酸乙酯＝10:1)得到油状液体产物32.2mg，收率59％。
[α]D 22.1-13.67(c 0.70,CHCl3,80％ee).1H NMR(400MHz,CDCl3)δ7.32-7.28(m,2H),7.23-7.19(m,3H),5.05-5.02(m,1H),4.21-4.07(m,2H),3.39(q,J＝7.6Hz,1H),2.96(t,J＝7.2Hz,2H),2.66(t,J＝7.6Hz,2H),2.08-1.99(m,1H),1.89-1.81(m,1H),1.75-1.74(m,3H),1.63-1.62(m,3H)；13C NMR(100MHz,CDCl3)δ172.5,140.2,138.7,128.5,128.2,126.4,120.6,117.6,60.9,35.7,32.2,30.9,26.6,25.5,18.1.HRMS:m/z(ESI)理论值[M+H]+:272.1645,检测值:272.1651.IR(neat,cm-1):2925,1705,1452,1161,700.HPLC(OD-H,0.46*25cm,5μm,hexane/isopropanol＝8/2,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝6.87min(minor)and 7.70min(major).
化合物I’-47：
该反应按照通用操作步骤2进行，柱层析分离(石油醚：乙酸乙酯＝10:1)得到油状液体产物22.0mg，收率56％。
[α]D 28.8-6.15(c 1.00,CHCl3,93％ee).1H NMR(400MHz,CDCl3)δ7.37-7.27(m,5H),6.72(d,J＝15.6Hz,1H),6.03(dd,J＝16.0,6.8Hz,1H),5.84-5.74(m,1H),5.13-5.06(m,2H),3.48-3.43(m,1H),2.34-2.26(m,2H),1.91-1.84(m,2H)；13C NMR(100MHz,CDCl3)δ136.1,135.7,133.5,128.7,128.3,126.5,122.8,119.9,116.6,33.6,32.3,30.7.HRMS:m/z(EI)理论值[M]+:197.1204,检测值:197.1208.IR(neat,cm-1):3028,2928,1727,1642,1601,1496,1450,1323,1261,1177,1071,993,966,917,747,695.HPLC(IF-3,0.46*15cm,3μm,hexane/isopropanol＝99/1,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝7.64min(minor)and 8.19min(major).
化合物I’-48：
该反应按照通用操作步骤2进行，柱层析分离(石油醚：乙酸乙酯＝10:1)得到油状液体产物19.5mg，收率48％。
[α]D 27.8-7.73(c 0.30,CHCl3,91％ee).1H NMR(400MHz,CDCl3)δ7.19(d,J＝5.2Hz,1H),7.04-7.03(m,1H),6.99-6.97(m,1H),6.17(d,J＝6.8Hz,1H),3.62-3.58(m,1H),2.85-2.78(m,1H),2.64-2.57(m,1H),2.14-1.64(m,6H)；13C NMR(100MHz,CDCl3)δ145.8,141.7,127.6,124.9,123.6,121.4,121.2,32.0,30.6,30.5,29.6,25.4.HRMS:m/z(EI)理论值[M]+:203.0769检测值:203.0773.IR(neat,cm-1):2930,2862,1706,1651,1518,1413,1236,1081,1059,855,723,588,552.HPLC(IC,0.46*25cm,5μm,hexane/isopropanol＝95/5,flow0.7mL/min,detection at 214nm)保留时间(retention time)＝12.93min(minor)and13.80min(major).
化合物I’-49：
该反应按照通用操作步骤1进行，柱层析分离(石油醚：乙酸乙酯＝10:1)得到油状液体产物40.5mg，收率81％。
[α]D 26.5-130.70(c 1.00,CHCl3,99％ee).1H NMR(400MHz,CDCl3)δ7.40(d,J＝8.4Hz,2H),7.34(d,J＝8.4Hz,2H),4.25(s,1H),2.51(d,J＝14.4Hz,1H),2.33-2.23(m,1H),2.17(d,J＝12.0Hz,1H),1.90-1.81(m,3H),1.77-1.66(m,1H),1.37-1.27(m,1H)；13CNMR(100MHz,CDCl3)δ151.3(d,J＝246.3Hz),135.5(d,J＝2.6Hz),129.8(d,J＝3.7Hz),129.4(d,J＝30.9Hz),128.7,119.9(d,J＝2.6Hz),112.9(d,J＝15.4Hz),30.0,29.5(d,J＝2.1Hz),26.9(d,J＝10.6Hz),25.3(d,J＝2.1Hz),22.2.19F NMR(376MHz,CDCl3)δ-97.52(s).HRMS:m/z(EI)理论值[M]+:249.0721,检测值:249.0718.IR(neat,cm-1):2934,2856,1690,1590,1487,1446,1365,1279,1200,1086,1039,902,833.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝9/1,flow 0.7mL/min,detection at 214nm)保留时间(retentiontime)＝5.79min(minor)and 6.35min(major).
化合物I’-50：
该反应按照通用操作步骤2进行，柱层析分离(石油醚：乙酸乙酯＝10:1)得到白色固体产物33.0mg，收率51％。
[α]D 26.3-58.70(c 0.80,CHCl3,82％ee).1H NMR(400MHz,CDCl3)δ8.12-8.09(m,2H),7.65-7.60(m,1H),7.52-7.48(m,2H),3.91(s,1H),2.58-2.52(m,1H),2.33-2.29(m,1H),2.18-2.15(m,1H),2.03-1.95(m,1H),1.81-1.63(m,9H),1.46-1.24(m,5H),1.14-1.07(m,1H)；13C NMR(100MHz,CDCl3)δ164.5,147.4,133.5,130.1,129.2,128.6,120.3,120.0,39.9,30.9,30.4,30.3,29.8,26.1,26.0,25.6,25.5,25.3,22.4.HRMS:m/z(EI)理论值[M]+:323.1885,检测值:323.1891.IR(neat,cm-1):2926,2855,1732,1448,1274,1250,1236,1219,1173,1138,1126,1089,1066,1024,995,862,800,704,662.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝9/1,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝14.42min(major)and 17.57min(minor).
化合物I’-51：
该反应按照通用操作步骤2进行，柱层析分离(石油醚：乙酸乙酯＝10:1)得到白色固体产物44.1mg，收率60％。
[α]D 25.9-6.89(c 0.50,CHCl3,82％ee).1H NMR(400MHz,CDCl3)δ7.45-7.42(m,6H),7.32-7.28(m,6H),7.25-7.22(m,3H),5.95-5.91(m,1H),5.72(dd,J＝15.2,6.0Hz,1H),3.66-3.65(m,2H),3.24(q,J＝6.0Hz,1H),1.77-1.72(m,2H),1.09(t,J＝7.2Hz,3H)；13CNMR(100MHz,CDCl3)δ143.9,131.0,128.5,127.9,127.1,124.3,120.2,86.9,63.6,35.5,26.4,11.2.HRMS:m/z(ESI)理论值[M+Na]+:390.1828,检测值:390.1828.IR(neat,cm-1):2961,2926,2854,1447,1032,798,699.HPLC(IG,0.46*25cm,5μm,hexane/isopropanol＝99/1,flow0.7mL/min,detection at 214nm)保留时间(retention time)＝13.75min(minor)and 15.56min(major).
化合物I’-52：
该反应按照通用操作步骤2进行，柱层析分离(石油醚：乙酸乙酯＝10:1)得到白色固体产物42.7mg，收率54％。
[α]D 26.8-14.62(c 0.50,CHCl3,90％ee).1H NMR(400MHz,CDCl3)δ7.75-7.71(m,4H),7.58-7.46(m,6H),5.82-5.77(m,1H),5.45-5.39(m,1H),3.17-3.11(m,3H),1.61-1.53(m,2H),0.91(t,J＝7.2Hz,3H)；13C NMR(100MHz,CDCl3)δ132.5,132.1(d,J＝2.8Hz),132.0(d,J＝3.5Hz),129.9(d,J＝12.1Hz),128.8(d,J＝4.9Hz),128.6(d,J＝5.7Hz),123.3(d,J＝8.7Hz),119.7(d,J＝1.1Hz),35.5(d,J＝2.1Hz),34.8,34.1,26.3(d,J＝1.9Hz),10.9.31P NMR(165MHz,CDCl3)δ30.2.HRMS:m/z(EI)理论值[M]+:309.1283,检测值:309.1276.IR(neat,cm-1):2936,2361,1436,1182,976,800,691,511.HPLC(IC-3,0.46*15cm,3μm,hexane/isopropanol＝6/4,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝19.50min(major)and 25.71min(minor).
化合物I’-53：
该反应按照通用操作步骤2进行，柱层析分离(石油醚：乙酸乙酯＝10:1)得到白色固体产物49.6mg，收率65％。
[α]D 27.7–21.19(c 0.30,CHCl3,82％ee).1H NMR(400MHz,CDCl3)δ7.51-7.49(m,6H),7.45-7.35(m,9H),5.87-5.78(m,1H),5.13(dd,J＝15.2,7.2Hz,1H),3.08(q,J＝7.2Hz,1H),2.36(d,J＝8.0Hz,2H),1.55-1.25(m,4H),0.84(t,J＝7.6Hz,3H)；13C NMR(100MHz,CDCl3)δ135.6,133.9,129.8,129.7,127.9,124.0,120.6,35.3,33.8,19.7,19.5,13.4.HRMS:m/z(EI)理论值[M]+:381.1913,检测值:381.1924.IR(neat,cm-1):2960,1421,1192,976,826,732,691.HPLC(IC-3,0.46*15cm,3μm,hexane/isopropanol＝98/2,flow0.7mL/min,detection at 214nm)保留时间(retention time)＝8.59min(minor)and8.97min(major).
化合物I’-54：
该反应按照通用操作步骤2进行，柱层析分离(石油醚：乙酸乙酯＝10:1)得到白色固体产物27.7mg，收率65％。
[α]D 27.0-18.38(c 0.30,CHCl3,85％ee).1H NMR(400MHz,CDCl3)δ7.94(d,J＝7.6Hz,1H),7.78-7.69(m,2H),7.64-7.60(m,1H),5.55(d,J＝9.6Hz,1H),3.98-3.92(m,1H),1.95-1.84(m,2H),1.16(t,J＝7.6Hz,3H)；13C NMR(100MHz,CDCl3)δ165.7,147.7,138.3,134.9,130.9,125.8,124.8,120.4,119.7,101.3,29.6,26.8,11.4.HRMS:m/z(EI)理论值[M]+:213.0790,检测值:213.0794.IR(neat,cm-1):2929,2360,1788,1464,976,761,692,550.HPLC(IC-3,0.46*15cm,3μm,hexane/isopropanol＝7/3,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝15.51min(minor)and 22.57min(major).
化合物I’-55：
该反应按照通用操作步骤2进行，柱层析分离(石油醚：乙酸乙酯＝10:1)得到白色固体产物33.8mg，收率62％。
[α]D 26.9-75.35(c 0.60,CHCl3,92％ee).1H NMR(400MHz,CDCl3)δ7.98-7.95(m,2H),7.87-7.83(m,2H),5.12(dd,J＝26.4,9.6Hz,1H),3.77-3.71(m,1H),1.92-1.76(m,2H),1.66-1.56(m,2H),1.02(t,J＝7.2Hz,3H)；13C NMR(100MHz,CDCl3)δ164.7(d,J＝2.1Hz),142.3(d,J＝269.5Hz),135.3,131.2,124.5,119.3(d,J＝2.2Hz),104.9(d,J＝20.4Hz),35.0(d,J＝1.7Hz),26.8,20.0,13.4.19F NMR(376MHz,CDCl3)δ-92.56(d,J＝25.9Hz).HRMS:m/z(EI)理论值[M]+:272.0961,检测值:272.0965.IR(neat,cm-1):2962,1797,1736,1467,1364,1079,904,881,796,529.HPLC(OJ-H,0.46*25cm,5μm,hexane/isopropanol＝8/2,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝11.32min(minor)and13.83min(major).
化合物I’-56：
该反应按照通用操作步骤2进行，柱层析分离(石油醚：乙酸乙酯＝10:1)得到油状液体产物49.1mg，收率65％。
[α]D 26.4-404.83(c 1.00,CHCl3,99％de).1H NMR(400MHz,CDCl3)δ7.16(d,J＝10.4Hz,1H),6.38(d,J＝10.4Hz,1H),5.90(s,1H),5.75(dd,J＝15.2,10.0Hz,1H),5.12-5.05(m,2H),4.34(d,J＝5.2Hz,1H),3.11(dd,J＝14.4,7.2Hz,1H),2.81-2.59(m,5H),2.23-2.14(m,2H),2.02-1.97(m,5H),1.80-1.37(m,4H),0.97(s,3H)；13C NMR(100MHz,CDCl3)δ193.2,170.5,154.4,147.3,145.2,132.7,123.1,122.2,120.1,119.3,118.6,91.6,50.1,48.4,38.6,38.3,35.1,31.4,26.8,26.6,25.3,22.5,21.6,16.4.HRMS:m/z(EI)理论值[M]+:377.1991,检测值:377.1988.IR(neat,cm-1):2943,1726,1658,1576,1435,1371,1320,1234,1162,1019,912,789,727,652.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝8/2,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝7.11min(minor)and 7.75min(major).
化合物I’-57：
该反应按照通用操作步骤1进行，5mmol反应，柱层析分离(石油醚：乙酸乙酯＝10:1)得到油状液体产物1.2g，收率60％。
[α]D 27.0-95.22(c 1.00,CHCl3,de>97％).1H NMR(400MHz,CDCl3)δ5.61(s,1H),5.21-5.17(m,1H),3.46(dd,J＝4.4,2.0Hz,1H),2.78-2.71(m,1H),2.60(s,1H),2.21-1.20(m,22H),0.95(s,3H),0.79-0.73(m,1H)；13C NMR(100MHz,CDCl3)δ170.8,169.5,137.6,126.0,120.4,84.0,83.1,75.0,69.1,49.1,47.8,47.0,38.4,37.3,37.1,35.6,34.0,32.6,26.9,25.2,24.7,23.1,21.4,21.2,13.5.HRMS:m/z(ESI)理论值[M+NH4]+:427.2591,检测值:427.2592.IR(neat,cm-1):2941,1733,1445,1369,1233,1020,906,730.
化合物I’-58：
该反应按照通用操作步骤1进行，0.2mmol反应，柱层析分离(石油醚：乙酸乙酯＝10:1)得到油状液体产物4.2mg，收率63％。
[α]D 26.8-59.16(c 0.70,CHCl3,de>97％).1H NMR(400MHz,CDCl3)δ7.50(d,J＝1.2Hz,1H),6.06(d,J＝5.6Hz,1H),5.85-5.83(m,1H),4.75-4.64(m,2H),3.80(s,3H),3.64-3.57(m,2H),3.25-3.21(dd,J＝6.0,7.6Hz,1H),2.16(s,3H),2.12(s,3H)；13C NMR(100MHz,CDCl3)δ170.3,168.9,166.2,153.2,141.4,126.4,119.0,108.1,89.9,60.4,51.7,45.8,40.1,38.7,20.8,20.7.HRMS:m/z(ESI)理论值[M+Na]+:358.0897,检测值:358.0895.IR(neat,cm-1):2956,1739,1708,1633,1437,1368,1288,1224.1181,1087,1044,1617,967,893,795,766,604,540,509,432.
化合物I’-59：
该反应按照通用操作步骤1进行，0.2mmol反应，柱层析分离(石油醚：乙酸乙酯＝10:1)得到白色固体产物47.5mg，收率61％。
[α]D 26.7-43.08(c 0.70,CHCl3,de>97％).1H NMR(400MHz,CDCl3)δ7.12(dd,J＝15.6,3.6Hz,1H),5.73(dd,J＝15.6,1.6Hz,1H),5.66(dd,J＝15.2,9.6Hz,1H),5.44(dd,J＝15.2,9.6Hz,1H),5.28-5.24(m,1H),5.17-5.13(m,1H),4.94-4.87(m,1H),3.33-3.28(m,1H),2.57-2.49(m,1H),2.40-2.33(m,1H),2.25-2.17(m,1H),2.13-1.93(m,9H),1.89-1.60(m,3H),1.31(d,J＝6.0Hz,3H),1.26-1.20(m,1H)；13C NMR(100MHz,CDCl3)δ170.4,169.7,165.1,146.8,139.9,124.9,119.9,118.6,75.7,75.1,70.9,49.6,43.5,39.5,38.4,33.7,31.2,29.7,21.3,20.7,20.6.HRMS:m/z(EI)理论值[M]+:389.1838,检测值:389.1844.IR(neat,cm-1):2962,2924,2854,1711,1260,1229,1089,1018,866,798.
化合物I’-60：
该反应按照通用操作步骤2进行，0.1mmol反应，柱层析分离(石油醚：乙酸乙酯＝10:1)得到油状液体产物29mg，收率51％。
[α]D 26.7-2.30(c 0.30,CHCl3,74％de).1H NMR(400MHz,CDCl3)δ7.46-744(m,6H),7.32-7.28(m,6H),7.24-7.22(m,3H),5.70(t,J＝6.4Hz,1H),3.67-3.66(m,2H),3.08(t,J＝7.6Hz,1H),1.70-1.64(m,2H),1.57-1.02(m,20H),0.89-0.83(m,12H)；13C NMR(100MHz,CDCl3)δ144.0,131.5,128.6,127.8,127.0,126.7,120.5,86.9,60.8,40.6,39.3,37.3,37.2,37.0,34.2,22.7,32.4,29.0,27.9,24.8,24.3,22.7,22.6,19.7,19.6,14.2.HRMS:m/z(ESI)理论值[M+NH4]+:581.4476,检测值:581.4471.IR(neat,cm-1):2952,2924,2866,2323,1490,1461,1448,1378,1366,1219,1182,1154,1049,1031,1002,987,942,898,761,744,703,670,649,632,479.HPLC(OD-H,0.46*25cm,5μm,hexane/isopropanol＝99/1,flow0.7mL/min,detection at 214nm)保留时间(retention time)＝6.68min(major)and6.98min(minor).
化合物I’-61：
该反应按照通用操作步骤1进行，0.2mmol反应，柱层析分离(石油醚：乙酸乙酯＝10:1)得到白色固体产物33.5mg，收率43％。
[α]D 26.5-63.13(c 1.00,CHCl3,93％ee).1H NMR(400MHz,CDCl3)δ7.16-7.02(m,8H),3.79(s,1H),2.63(d,J＝14.0Hz,1H),2.30-2.22(m,7H),2.08-2.04(m,1H),1.93-1.82(m,3H),1.60-1.57(m,1H),1.92-1.38(m,1H)；13C NMR(100MHz,CDCl3)δ169.4,149.8,149.7,138.4,138.3,137.8,132.9,130.3,130.2,121.8,121.3,120.9,32.8,31.2,28.6,27.6,22.5,21.1.HRMS:m/z(EI)理论值[M]+:389.1627,检测值:389.1621.IR(neat,cm-1):2934,1754,1653,1595,1501,1368,1192,1010,910,847,727,665.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝7/3,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝8.95min(minor)and 10.53min(major).
化合物I’-62：
该反应按照通用操作步骤1进行，0.2mmol反应，柱层析分离(石油醚：乙酸乙酯＝10:1)得到白色固体产物41.7mg，收率41％。
[α]D 26.5-0.85(c 1.00,CHCl3,80％de).1H NMR(400MHz,CDCl3)δ7.45(d,J＝8.8Hz,2H),7.37(d,J＝8.4Hz,2H),5.41(dd,J＝33.6,9.2Hz,1H),3.91-3.84(m,1H),2.69(t,J＝14.4Hz,1H),2.33(td,J＝14.4,5.2Hz,1H),2.19-2.14(m,1H),2.08-1.03(m,29H),0.75(s,3H)；13C NMR(100MHz,CDCl3):δ213.4,157.6(d,J＝251.9Hz),135.9,129.2(d,J＝28.4Hz),128.9(d,J＝1.7Hz),125.7(d,J＝6.7Hz),120.1,101.7(d,J＝15.0Hz),56.3(d,J＝19.8Hz),44.3,43.0,42.4,40.7,40.1,39.7,37.2,37.0,35.5,34.9,34.6,28.3,26.6,25.8,24.9,24.8,24.2,22.7,21.2,18.3,12.2.19F NMR(376MHz,CDCl3)δ-114.49(d,J＝32.7Hz).The de value was detected by 19F NMR.HRMS:m/z(ESI)理论值[M+H]+:510.2933检测值:510.2940.IR(neat,cm-1):2933,1770,1707,1448,1386,1092,997,912,826,707.
化合物I’-63：
该反应按照通用操作步骤1进行，0.2mmol反应，柱层析分离(石油醚：乙酸乙酯＝10:1)得到白色固体产物74.8mg，收率63％。
[α]D 28.3-15.13(c 1.00,CHCl3,91％de).1H NMR(400MHz,CDCl3)δ7.39-7.26(m,5H),6.74(d,J＝16.0Hz,1H),6.04(dd,J＝16.0Hz,J＝6.4Hz,1H),5.38-5.37(m,1H),4.63-4.60(m,1H),3.46(q,J＝6.0Hz,1H),2.37-2.30(m,4H),2.03-1.78(m,9H),1.63-0.86(m,33H),0.68(s,3H)；13C NMR(100MHz,CDCl3):δ172.1,139.5,135.6,133.5,128.7,128.3,126.5,122.7,122.6,119.8,74.1,56.6,56.1,49.9,42.3,39.7,39.5,38.1,36.9,36.5,36.1,35.8,34.2,33.7,32.5,31.9,31.8,28.2,28.0,27.7,24.2,23.8,22.8,22.5,22.1,21.0,19.3,18.7,11.8.HRMS:m/z(ESI)理论值[M+H]+:598.4624检测值:598.4629.IR(neat,cm-1):2943,1721,1443,1378,1225,1143,864,700.HPLC(AY-3,0.46*15cm,3μm,hexane/isopropanol＝8/2,flow0.7mL/min,detection at 214nm)保留时间(retentiontime)＝7.69min(major)and 9.75min(minor).
化合物I’-64：
该反应按照通用操作步骤1进行，0.2mmol反应，柱层析分离(石油醚：乙酸乙酯＝10:1)得到白色固体产物44.0mg，收率51％。
(1R)-21c(44.0mg,51％yield,62％conversion of starting material,whitesolid).[α]D 28.464.97(c 1.00,CHCl3,95％de)
1H NMR(400MHz,CDCl3)δ7.40-7.31(m,5H),5.86(d,J＝5.2Hz,1H),4.58(t,J＝8.4Hz,1H),4.39(s,1H),2.17-2.04(m,5H),1.82-0.66(m,24H)；13C NMR(100MHz,CDCl3):δ171.3,134.4,130.9,128.9,128.1,127.5,125.8,119.1,82.8,53.6,50.6,44.5,42.4,41.4,39.8,36.8,35.2,34.4,31.1,30.5,28.2,27.4,23.4,21.2,20.5,12.0,11.8.HRMS:m/z(ESI)理论值[M+NH4]+:449.3163,检测值:449.3162.IR(neat,cm-1):2917,2882,1731,1449,1245,1044,1029,801,529,420.HPLC(IC-3,0.46*15cm,3μm,hexane/isopropanol＝8/2,flow 0.7mL/min,detection at 214nm)保留时间(retention time)＝14.03min(major)and 14.96min(minor).
实施例3式A化合物对取代反应的影响
按照实施例2中操作1的方法，将式A化合替换为如下化合物，反应结果如下所示。
实施例4双噁唑啉配体对取代反应的影响
按照实施例2中操作1的方法，将双噁唑啉配体替换为如下的溶剂，反应结果如下所示。
实施例5铜催化剂对取代反应的影响
按照实施例2中操作1的方法，采用如下的铜催化剂，反应结果如下所示。
实施例6溶剂对取代反应的影响
按照实施例2中操作1的方法，采用如下溶剂，反应结果如下所示。
对比例1
按照实施例2中操作1的方法，采用如下化合物作为氧化剂，收率较低，仅有12％。
Claims (20)
1.一种如式A所示的化合物：
其中，R1a、R1b和R1c各自独立地为C1～C4烷基或者苯基；
R2a为C6～C14芳基或被一个或多个R2a-1取代的C6～C14芳基；
R2a-1为卤素、C1～C4烷基、卤素取代的C1～C4烷基、C1～C4烷氧基或C6～C14芳基；当R2a-1为多个时，R2a-1相同或者不同；
且所述的式A所示的化合物不为
2.如权利要求1所述的如式A所示的化合物，其特征在于，式A中，当R1a、R1b和R1c各自独立地为C1～C4烷基，所述的C1～C4烷基为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基；
或，式A中，当R2a为C6～C14芳基时，所述的C6～C14芳基为苯基、萘基、蒽基或菲基；
或，式A中，当R2a为R2a-1取代的C6～C14芳基时，所述的R2a-1为1个；
或，式A中，当R2a为R2a-1取代的C6～C14芳基时，所述的C6～C14芳基为苯基、萘基、蒽基或菲基；
或，式A中，当R2a-1为卤素时，所述的卤素独立地为氟、氯、溴或碘；
或，当R2a-1为C1～C4烷基时，所述的C1～C4烷基为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基；
或，式A中，当R2a-1为C1～C4烷氧基时，所述的C1～C4烷氧基为甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基或叔丁氧基；
或，式A中，当R2a-1为C6～C14芳基时，所述的C6～C14芳基为苯基、萘基、蒽基或菲基。
3.如权利要求2所述的如式A所示的化合物，其特征在于，式A中，当R1a、R1b和R1c各自独立地为C1～C4烷基时，所述的C1～C4烷基为甲基；
或，式A中，当R2a为C6～C14芳基时，所述的C6～C14芳基为苯基或萘基；
或，式A中，当R2a为R2a-1取代的C6～C14芳基时，所述的C6～C14芳基为苯基；
或，式A中，当R2a-1为卤素时，所述的卤素为氟或氯；
或，式A中，当R2a-1为C1～C4烷基时,所述的C1～C4烷基为甲基或叔丁基；
或，式A中，当R2a-1为C1～C4烷氧基时，所述的C1～C4烷氧基为甲氧基；
或，式A中，当R2a-1为C6～C14芳基时，所述的C6～C14芳基为苯基。
4.如权利要求2所述的如式A所示的化合物，其特征在于，式A中，当R2a为R2a-1取代的C6～C14芳基时，R2a-1位于磺酰胺的对位；
或，式A中，R2a-1为卤素或卤素取代的C1～C4烷基；
或，式A中，
为
5.如权利要求1所述的如式A所示的化合物，其特征在于，其为如下任一化合物：
6.如权利要求1～5任一项所述的如式A所示的化合物的制备方法，其特征在于，其包括以下步骤：有机溶剂中，在碱存在下，将如式B所示的化合物和氟化试剂进行如下所示的氟化反应，制得所述的如式A所示的化合物；
7.一种烯丙基腈类化合物的制备方法，其特征在于，其包括以下步骤：溶剂中，在铜催化剂、双噁唑啉配体和如权利要求1～5任一项所述的如式A所示的化合物的存在下，将含有如式II所示的结构片段的烯丙基化合物与如式III所示的氰基化试剂进行如下式的取代反应，得到含有如式I所示的结构片段的烯丙基腈类化合物即可；
所述的取代反应中，所述的铜催化剂为碘化亚铜、氯化亚铜、溴化亚铜、醋酸亚铜、噻吩甲酸亚铜、四乙腈六氟磷酸铜、四乙腈三氟甲磺酸铜、四乙腈四氟硼酸铜、和三氟甲磺酸铜中的一种或多种；
所述的取代反应中，所述的双噁唑啉配体为
其中R4a、R4b、R5a和R5b独立为氢、C1～C4烷基；“R4a和R4b”、“R5a和R5b”还可与其相连的碳一起形成的C3～C7环烷基；
其中，用*标注的碳是指S构型手性碳、R构型手性碳或非手性碳；R3a、R3b和R3c各自独立地为C1～C4烷基。
8.如权利要求7所述的制备方法，其特征在于，式III中，当R3a、R3b和R3c独立地为C1～C4烷基，所述的C1～C4烷基为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基；
或，所述的取代反应中，所述的溶剂为芳烃类溶剂、取代芳烃类溶剂、腈类溶剂、卤代烃类溶剂、醚类溶剂、酮类溶剂、酯类溶剂和酰胺类溶剂中的一种或多种；
或，所述的铜催化剂的用量为所述的含有如式II所示结构片段的烯丙基化合物的1～50％摩尔当量；
或，所述的双噁唑啉配体的用量为所述的含有如式II所示结构片段的烯丙基化合物的1～75％摩尔当量；
或，所述的取代反应中，所述的铜催化剂与所述的双噁唑啉配体的摩尔比为2.0:1～1.0:3；
或，所述的取代反应中，所述的含有如式II所示结构片段的烯丙基化合物的浓度为0.01～1.00mol/L；
或，所述的取代反应中，所述的如式A所示的化合物与所述的含有如式II所示结构片段的烯丙基化合物的摩尔比为1.0:1～4.0:1；
或，所述的取代反应中，所述的如式III所示的氰基化试剂与所述的含有如式II所示结构片段的烯丙基化合物的摩尔比为1.0:1～5.0:1；
或，所述的取代反应的温度为0～80℃；
或，所述的取代反应在保护气体下进行。
9.如权利要求8所述的制备方法，其特征在于，所述的取代反应中，所述的溶剂为芳烃类溶剂或取代芳烃类溶剂。
10.如权利要求8所述的制备方法，其特征在于，式III中，当R3a、R3b和R3c独立地为C1～C4烷基，所述的C1～C4烷基为甲基；
或，所述的取代反应中，当所述的溶剂为芳烃类溶剂时，所述的芳烃类溶剂为苯；
或，所述的取代反应中，当所述的溶剂为取代芳烃类溶剂时，所述的芳烃类溶剂为氯苯、溴苯、氟苯、三氟甲苯、四氟苯、六氟苯和三氟甲基苯中的一种或多种；
或，所述的取代反应中，当所述的溶剂为腈类溶剂时，所述的腈类溶剂为乙腈；
或，所述的取代反应中，当所述的溶剂为卤代烃类溶剂时，所述的卤代烃类溶剂为二氯甲烷；
或，所述的取代反应中，当所述的溶剂为醚类溶剂时，所述的醚类溶剂为四氢呋喃；
或，所述的取代反应中，当所述的溶剂为酮类溶剂时，所述的酮类溶剂为丙酮；
或，所述的取代反应中，当所述的溶剂为酯类溶剂时，所述的酯类溶剂为乙酸乙酯；
或，所述的取代反应中，当所述的溶剂为酰胺溶剂时，所述的酰胺溶剂为N,N-二甲基甲酰胺；
或，所述的取代反应中，所述的铜催化剂为溴化亚铜、噻吩甲酸亚铜、四乙腈六氟磷酸铜、四乙腈三氟甲磺酸铜和醋酸亚铜中的一种或多种；
或，所述的铜催化剂的用量为所述的含有如式II所示结构片段的烯丙基化合物的1～10％摩尔当量；
或，所述的取代反应中，所述的双噁唑啉配体中，“R4a和R4b”、“R5a和R5b”还可与其相连的碳一起形成的C3～C7环烷基；
或，当所述的双噁唑啉配体为
时，得到的如式I所示的结构片段的烯丙基腈类化合物
其中，用*标注的碳是R构型手性碳；
或，当所述的双噁唑啉配体为
时，得到的如式I所示的结构片段的烯丙基腈类化合物
其中，用*标注的碳是S构型手性碳；
或，所述的取代反应中，所述的含有如式II所示结构片段的烯丙基化合物的浓度为0.01～0.20mol/L；
或，所述的取代反应中，所述的如式A所示的化合物与所述的含有如式II所示结构片段的烯丙基化合物的摩尔比为2.5:1～3.0:1；
或，所述的取代反应中，所述的如式III所示的氰基化试剂与所述的含有如式II所示结构片段的烯丙基化合物的摩尔比为2.0:1～3.0:1；
或，所述的取代反应的温度为0～30℃；
或，当所述的取代反应在保护气体下进行时，所述的保护气体为氮气和/或氩气。
11.如权利要求10所述的制备方法，其特征在于，所述的取代反应中，当所述的溶剂为取代芳烃类溶剂时，所述的芳烃类溶剂为六氟苯；
或，所述的取代反应中，所述的铜催化剂为醋酸亚酮；
或，所述的取代反应中，所述的双噁唑啉配体为
12.如权利要求7～11任一项所述的制备方法，其特征在于，所述的含有如式II所示的结构片段的烯丙基化合物如式II’所示，相应地得到如式I’所示的含有所述的如式I所示的结构片段的烯丙基腈类化合物；
其中，R1、R2、R3和R4独立地为氢、卤素、C1～C20烷基、R1-1取代的C1～C20烷基、C2～C10烯基、C2～C10炔基、R1-2取代的C2～C10炔基、C3～C30环烷基、R1-3取代的C3～C30环烷基、C3～C30杂环烷基、R1-4取代的C3～C30杂环烷基、C6～C30芳基、R1-5取代的C6～C30芳基、C1～C30杂芳基、R1-6取代的C1～C30杂芳基、OR1-7、-SiMe2Ph、-SiPh3、
-(P＝O)Ph2或-NPhth；所述的C3～C30杂环烷基、所述的R1-4取代的C3～C30杂环烷基、所述的C1～C30杂芳基和R1-6取代的C1～C30杂芳基中的杂原子独立地为N、O和S中的一种或多种，杂原子数为1～3个；
R1-1、R1-2、R1-3、R1-4、R1-5和R1-6独立地为卤素、-OR1-1-1、-NPhth、-N3、-O(C＝O)R1-1-2、-(C＝O)Ph3、-(C＝O)OR1-1-3、C1～C4烷基、卤素取代的C1～C4烷基、-SCF3、卤素取代的C1～C4烷氧基、C1～C4烷氧基、C3～C10杂芳基、-NR1-1-4或-SiPh3；所述的C3～C10杂芳基的杂原子为N、O和S中的一种或多种，杂原子数为1～3个；R1-7为羟基保护基团；R1-1、R1-2、R1-3、R1-4、R1-5和R1-6独立地为1个或多个，当R1-1、R1-2、R1-3、R1-4、R1-5和R1-6独立地为多个时，R1-1、R1-2、R1-3、R1-4、R1-5和R1-6独立地相同或不同；
R1-1-1为羟基保护基团；R1-1-2为C1～C4烷基或苯基取代的C1～C4烷基；R1-1-3为C1～C4烷基或
R1-1-4为氨基保护基团；R1-1-4为1个或多个，当R1-1-4为多个时，R1-1-4相同或不同；
“R1和R2”、“R3和R4”还可与其相连的碳一起形成C3～C30环烷基、氧代的C3～C30环烯基、C3～C30杂环烷基、R2-1取代的C3～C30杂环烷基、
所述的C3～C30杂环烷基和R2-1取代的C3～C30杂环烷基的中杂原子独立地为N、O和S中的一种或多种，杂原子数为1～3个；
R2-1为氧代、氨基保护基团或苯基，当C3～C30杂环烷基中的杂原子为N，氨基保护基与C3～C30杂环烷基中的杂原子N连接；R2-1为1个或多个，当R2-1为多个时，R2-1相同或不同；
“R1和R3”、“R1和R4”、“R2和R3”、“R2和R4”还可与其相连的碳一起形成C3～C30亚环烯基、R3-1取代的C3～C30亚环烯基、C3～C30亚杂环烯基、
所述C3～C30杂环烯基中的杂原子独立地为N、O和S中的一种或多种，杂原子数为1～3个；
R3-1为氧代或羟基保护基团。
13.如权利要求12所述的制备方法，其特征在于，当R1和R2独立地为卤素时，所述的卤素为氟、氯、溴或碘；
或，当R1、R2、R3和R4独立地为C1～C20烷基时，所述的C1～C20烷基为C1～C4烷基；
或，当R4独立地为R1-1取代的C1～C20烷基时，所述的C1～C20烷基为C1～C12烷基；
或，当R4为R1-1取代的C1～C20烷基时，所述的C1～C20烷基为C1～C12烷基；
或，当R4为C2～C10烯基时，所述的C2～C10烯基为C2～C4烯基；
或，当R4为R1-3取代的C2～C10炔基时，所述的C2～C10炔基为C2～C4炔基；
或，当所述的R1和R2独立地为C3～C30环烷基，所述的C3～C30环烷基为C3～C6环烷基；
或，当所述的R1和R2独立地为R1-4取代的C3～C30杂环烷基时，所述的C3～C30杂环烷基中的杂原子为N；
或，当所述的R1和R2独立地为R1-4取代的C3～C30杂环烷基时，所述的C3～C30杂环烷基中的杂原子的个数为1个；
或，当所述的R1和R2独立地为R1-4取代的C3～C30杂环烷基时，所述的C3～C30杂环烷基为C3～C5杂环烷基；
或，当所述的R1和R2独立地为C6～C30芳基时，所述的C6～C30芳基为C6～C14芳基；
或，当所述的R1和R2独立地为R1-5取代的C6～C30芳基时，所述的C6～C30芳基为C6～C14芳基；
或，当所述的R1和R2独立地为C1～C30杂芳基，所述的C1～C30杂芳基为C3～C5杂芳基；
或，当所述的R1和R2独立地为C1～C30杂芳基，所述的C1～C30杂芳基中的杂原子为O或S；
或，当所述的R1和R2独立地为C1～C30杂芳基，所述的C1～C30杂芳基中的杂原子的个数为1个；
或，当所述的R1和R2独立地为R1-6取代的C1～C30杂芳基时，所述的C1～C30杂芳基中的杂原子为S或N；
或，当所述的R1和R2独立地为R1-6取代的C1～C30杂芳基时，所述的C1～C30杂芳基中的杂原子个数为1个；
或，当所述的R1和R2独立地为R1-6取代的C1～C30杂芳基时，所述的C1～C30杂芳基为C3～C10杂芳基；
或，当所述的R1-1、R1-2、R1-3、R1-4、R1-5和R1-6独立地为卤素，所述的卤素为氟、氯、溴或碘；
或，当R1-1、R1-2、R1-3、R1-4、R1-5和R1-6独立地为C1～C4烷基，所述的C1～C4烷基为甲基；
或，当R1-1、R1-2、R1-3、R1-4、R1-5和R1-6独立地为卤素取代的C1～C4烷基，所述的卤素取代的C1～C4烷基为三氟甲基；
或，当R1-1、R1-2、R1-3、R1-4、R1-5和R1-6独立地为卤素取代的C1～C4烷氧基，所述的卤素取代的C1～C4烷氧基为三氟甲氧基；
或，当R1-1、R1-2、R1-3、R1-4、R1-5和R1-6独立地为C1～C4烷氧基，所述的C1～C4烷氧基为甲氧基；
或，当R1-1、R1-2、R1-3、R1-4、R1-5和R1-6独立地为C3～C10杂芳基时，所述的C3～C10杂芳基为
或，当R1-1-1为羟基保护基或R1-7为羟基保护基团时，所述的羟基保护基团为乙酰基、
或，当R1-1-2为C1～C4烷基或苯基取代的C1～C4烷基时，所述的C1～C4烷基为甲基或乙基；
或，当R1-1-3为C1～C4烷基时，所述的C1～C4烷基为甲基；
或，当R1-1-4为氨基保护基团时，所述的氨基保护基团为
或，当“R1和R2”、或、“R3和R4”与其相连的碳一起形成C3～C30环烷基时，所述的C3～C30环烷基为C3～C10环烷基；
或，当“R1和R2”、或、“R3和R4”与其相连的碳一起形成所述的氧代的C3～C30环烯基时，所述的氧代的C3～C30环烯基为氧代的C3～C6环烯基；
或，当“R1和R2”、或、“R3和R4”与其相连的碳一起形成R2-1取代的C3～C30杂环烷基，所述的C3～C30杂环烷基中的杂原子为O或N；
或，“R1和R2”、或、“R3和R4”与其相连的碳一起形成R2-1取代的C3～C30杂环烷基，所述的C3～C30杂环烷基中的杂原子的个数为1个；
或，当“R1和R2”、或、“R3和R4”与其相连的碳一起形成R2-1取代的C3～C30杂环烷基，所述的C3～C30杂环烷基中为C3～C5杂环烷基；
或，当R2-1为氨基保护基时，所述的氨基保护基团为
或，当R2-1为苯基时，所述的苯基与所述的C3～C30杂环烷基并环连接；
或，当“R1和R3”、“R1和R4”、“R2和R3”、或、“R2和R4”与其相连的碳一起形成C3～C30亚环烯基时，所述的C3～C30亚环烯基为C3～C7亚环烯基；
或，当R3-1为羟基保护基团时，所述的羟基保护基团为乙酰基。
14.如权利要求13所述的制备方法，其特征在于，当R1和R2独立地为卤素时，所述的卤素为氟或溴；
或，当R1、R2、R3和R4独立地为C1～C20烷基时，所述的C1～C20烷基为甲基、乙基、正丙基或正丁基；
或，当R4独立地为R1-1取代的C1～C20烷基时，所述的C1～C20烷基为甲基、乙基或正十二烷基；
或，当R4为R1-1取代的C1～C20烷基时，所述的C1～C20烷基为乙基或正十二烷基；
或，当R4为C2～C10烯基时，所述的C2～C10烯基为
或，当R4为R1-3取代的C2～C10炔基时，所述的C2～C10炔基为乙炔基；
或，当所述的R1和R2独立地为C3～C30环烷基时，所述的C3～C30环烷基为环己基；
或，当所述的R1和R2独立地为C6～C30芳基时，所述的C6～C30芳基为苯基或萘基；
或，当所述的R1和R2独立地为R1-5取代的C6～C30芳基时，所述的C6～C30芳基为苯基；
或，当“R1和R2”、或、“R3和R4”与其相连的碳一起形成C3～C30环烷基时，所述的C3～C30环烷基为环己基或环庚基；
或，当“R1和R2”、或、“R3和R4”与其相连的碳一起形成所述的氧代的C3～C30环烯基时，所述的氧代的C3～C30环烯基为
或，当“R1和R3”、“R1和R4”、“R2和R3”、或、“R2和R4”与其相连的碳一起形成C3～C30亚环烯基时，所述的C3～C30亚环烯基为亚环己烯基或亚环庚烯基。
15.如权利要求13所述的制备方法，其特征在于，当R1和R2独立地为R1-1取代的C1～C20烷基时，所述的R1-1取代的C1～C20烷基为“-NPhth、羟基保护基团、氨基保护基团、-(C＝O)Ph3或-SiPh3”取代的C1～C4烷基；
或，当R4为R1-1取代的C1～C20烷基时，所述的R1-1取代的C1～C20烷基为“C1～C4烷基、-N3、羟基保护基团、-NPhth、卤素、-O(C＝O)R1-1-2或-(C＝O)OR1-1-3”取代的C1～C12烷基；
或，当R4为R1-3取代的C2～C10炔基时，所述的R1-3取代的C2～C10炔基为“-SiPh3”取代的C2～C4炔基；
或，当所述的R1和R2独立地为R1-4取代的C3～C30杂环烷基时，所述R1-4取代的C3～C30杂环烷基为“氧代、苯基或氨基保护基”取代的C3～C5杂环烷基；
或，当所述的R1和R2独立地为R1-5取代的C6～C30芳基时，所述的R1-5取代的C6～C30芳基为“卤素、羟基保护基、卤素取代的C1～C4烷基、-SCF3、卤素取代的C1～C4烷氧基、C1～C4烷氧基或C3～C10杂芳基”取代的C6～C14芳基；
或，当所述的R1和R2独立地为C1～C30杂芳基，所述的C1～C30杂芳基为“杂原子为O或S”的C3～C10杂芳基；
或，当所述的R1和R2独立地为R1-6取代的C1～C30杂芳基时，所述的R1-6取代的C1～C30杂芳基为“卤素或C1～C4烷氧基”取代的C3～C10杂芳基；
或，当“R1和R2”、或、“R3和R4”与其相连的碳一起形成R2-1取代的C3～C30杂环烷基，所述的“氧代、氨基保护基或苯基”取代的C3～C5杂环烷基；
或，当“R1和R3”、“R1和R4”、“R2和R3”、或、“R2和R4”与其相连的碳一起形成R3-1取代的C3～C30亚环烯基时，所述的R3-1取代的C3～C30亚环烯基可以为羟基保护基取代的C3～C7亚环烯基。
16.如权利要求15所述的制备方法，其特征在于，当R1和R2独立地为R1-1取代的C1～C20烷基时，所述的R1-1取代的C1～C20烷基为
或，当R4为R1-1取代的C1～C20烷基时，所述的R1-1取代的C1～C20烷基为
或，当R4为R1-3取代的C2～C10炔基时，所述的R1-3取代的C2～C10炔基为
或，当所述的R1和R2独立地为R1-4取代的C3～C30杂环烷基时，所述R1-4取代的C3～C30杂环烷基为
或，当所述的R1和R2独立地为R1-5取代的C6～C30芳基时，所述的R1-5取代的C6～C30芳基为
或，当所述的R1和R2独立地为C1～C30杂芳基，所述的C1～C30杂芳基为
或，当所述的R1和R2独立地为R1-6取代的C1～C30杂芳基时，所述的R1-6取代的C1～C30杂芳基为
或，当“R1和R2”、或、“R3和R4”与其相连的碳一起形成R2-1取代的C3～C30杂环烷基，所述的R2-1取代的C3～C30杂环烷基为
或，当“R1和R3”、“R1和R4”、“R2和R3”、或、“R2和R4”与其相连的碳一起形成R3-1取代的C3～C30亚环烯基时，所述的R3-1取代的C3～C30亚环烯基为
17.如权利要求13所述的制备方法，其特征在于，R1和R2中，一个为氢或卤素；所述的卤素为氟；
或，R3为氢；
或，R4为C1～C20烷基或R1-1取代的C1～C20烷基；
或，“R3和R4”与其相连的碳一起形成C3～C30环烷基。
18.如权利要求17所述的制备方法，其特征在于，当R4为R1-1取代的C1～C20烷基时，R3为H；R1和R2中，其中一个为氢，另一个为C6～C30芳基；所述的R1-1不为-(C＝O)OR1-1-2；
或，当R4为C1～C20烷基时，R3为H；R1和R2中，其中一个为H，另一个为C6～C30芳基、R1-1取代的C1～C20烷基、-SiMe2Ph、-NPhth或R1-2取代的C2～C10炔基，所述的R1-1为-SiPh3；
或，当R4为C1～C20烷基时，R3为H；R1和R2中，其中一个为C1～C20烷基或卤素，另一个为C6～C30芳基；所述的卤素为氟；
或，当“R3和R4”与其相连的碳一起形成C3～C30环烷基时，R1和R2中，其中一个为C6～C30芳基或R1-5取代的C6～C30芳基，另一个为卤素；所述的卤素为氟。
19.如权利要求18所述的制备方法，其特征在于，所述的如式II’所示的含有如式II所示的结构片段的烯丙基化合物为如下任一化合物：
和/或，所述的如式I’所示的含有如式I所示的结构片段的烯丙基腈类化合物为如下任一化合物：
20.一种如权利要求1～5任一项所述的如式A所示的化合物作为氧化剂在氰化反应中的应用；所述的应用中，所述的氰化反应用于制备如权利要求7～19任一项所述的含有如式I所示的结构片段的烯丙基腈类化合物；
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