CN112028919A - B (3)/B (3,6) -o-carborane alkylation method of compound - Google Patents
B (3)/B (3,6) -o-carborane alkylation method of compound Download PDFInfo
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- CN112028919A CN112028919A CN202010844238.8A CN202010844238A CN112028919A CN 112028919 A CN112028919 A CN 112028919A CN 202010844238 A CN202010844238 A CN 202010844238A CN 112028919 A CN112028919 A CN 112028919A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 37
- 230000029936 alkylation Effects 0.000 title claims abstract description 11
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 150000001408 amides Chemical class 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- GJLPUBMCTFOXHD-UPHRSURJSA-N (11z)-1$l^{2},2$l^{2},3$l^{2},4$l^{2},5$l^{2},6$l^{2},7$l^{2},8$l^{2},9$l^{2},10$l^{2}-decaboracyclododec-11-ene Chemical compound [B]1[B][B][B][B][B]\C=C/[B][B][B][B]1 GJLPUBMCTFOXHD-UPHRSURJSA-N 0.000 claims abstract description 12
- 125000000879 imine group Chemical group 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- -1 polyfluoroaryl Chemical group 0.000 claims description 10
- 125000002619 bicyclic group Chemical group 0.000 claims description 8
- 125000002541 furyl group Chemical group 0.000 claims description 8
- 125000001072 heteroaryl group Chemical group 0.000 claims description 8
- 125000004076 pyridyl group Chemical group 0.000 claims description 8
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 238000006880 cross-coupling reaction Methods 0.000 claims description 6
- 125000002950 monocyclic group Chemical group 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 6
- 125000001544 thienyl group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 238000001212 derivatisation Methods 0.000 claims description 5
- 229910000071 diazene Inorganic materials 0.000 claims description 5
- 125000002883 imidazolyl group Chemical group 0.000 claims description 5
- 125000001624 naphthyl group Chemical group 0.000 claims description 5
- 125000000335 thiazolyl group Chemical group 0.000 claims description 5
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001262 acyl bromides Chemical group 0.000 claims description 4
- 150000001263 acyl chlorides Chemical class 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 claims description 3
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 3
- 150000001721 carbon Chemical class 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000001041 indolyl group Chemical group 0.000 claims description 3
- 125000005499 phosphonyl group Chemical group 0.000 claims description 3
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 3
- 125000002098 pyridazinyl group Chemical group 0.000 claims description 3
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 3
- 229960002317 succinimide Drugs 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 2
- 125000003147 glycosyl group Chemical group 0.000 claims description 2
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 229940078552 o-xylene Drugs 0.000 claims description 2
- 125000002971 oxazolyl group Chemical group 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001042 pteridinyl group Chemical group N1=C(N=CC2=NC=CN=C12)* 0.000 claims description 2
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 claims description 2
- 125000005493 quinolyl group Chemical group 0.000 claims description 2
- 229940124530 sulfonamide Drugs 0.000 claims description 2
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- 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 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims 1
- 238000007306 functionalization reaction Methods 0.000 abstract description 7
- 230000004913 activation Effects 0.000 abstract description 6
- 125000000524 functional group Chemical group 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
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- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 178
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 29
- 238000005160 1H NMR spectroscopy Methods 0.000 description 29
- 238000005481 NMR spectroscopy Methods 0.000 description 29
- 239000010948 rhodium Substances 0.000 description 14
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 229910052796 boron Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- HUWSZNZAROKDRZ-RRLWZMAJSA-N (3r,4r)-3-azaniumyl-5-[[(2s,3r)-1-[(2s)-2,3-dicarboxypyrrolidin-1-yl]-3-methyl-1-oxopentan-2-yl]amino]-5-oxo-4-sulfanylpentane-1-sulfonate Chemical compound OS(=O)(=O)CC[C@@H](N)[C@@H](S)C(=O)N[C@@H]([C@H](C)CC)C(=O)N1CCC(C(O)=O)[C@H]1C(O)=O HUWSZNZAROKDRZ-RRLWZMAJSA-N 0.000 description 5
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
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- 230000000694 effects Effects 0.000 description 4
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- 125000006575 electron-withdrawing group Chemical group 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
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- 125000001424 substituent group Chemical group 0.000 description 3
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- DNXHEGUUPJUMQT-UHFFFAOYSA-N (+)-estrone Natural products OC1=CC=C2C3CCC(C)(C(CC4)=O)C4C3CCC2=C1 DNXHEGUUPJUMQT-UHFFFAOYSA-N 0.000 description 2
- 238000004293 19F NMR spectroscopy Methods 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DNXHEGUUPJUMQT-CBZIJGRNSA-N Estrone Chemical compound OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 DNXHEGUUPJUMQT-CBZIJGRNSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 125000001584 benzyloxycarbonyl group Chemical group C(=O)(OCC1=CC=CC=C1)* 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 210000004899 c-terminal region Anatomy 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
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- 229960003399 estrone Drugs 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
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- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000002560 therapeutic procedure Methods 0.000 description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- 125000003088 (fluoren-9-ylmethoxy)carbonyl group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000013175 Crataegus laevigata Nutrition 0.000 description 1
- XPDXVDYUQZHFPV-UHFFFAOYSA-N Dansyl Chloride Chemical compound C1=CC=C2C(N(C)C)=CC=CC2=C1S(Cl)(=O)=O XPDXVDYUQZHFPV-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000006254 arylation reaction Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001295 dansyl group Chemical group [H]C1=C([H])C(N(C([H])([H])[H])C([H])([H])[H])=C2C([H])=C([H])C([H])=C(C2=C1[H])S(*)(=O)=O 0.000 description 1
- 238000010502 deborylation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007350 electrophilic reaction Methods 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001146 hypoxic effect Effects 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000003589 local anesthetic agent Substances 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
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- 210000000056 organ Anatomy 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- UYWQUFXKFGHYNT-UHFFFAOYSA-N phenylmethyl ester of formic acid Natural products O=COCC1=CC=CC=C1 UYWQUFXKFGHYNT-UHFFFAOYSA-N 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
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- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
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- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical group C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 description 1
- 125000001981 tert-butyldimethylsilyl group Chemical group [H]C([H])([H])[Si]([H])(C([H])([H])[H])[*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 210000004881 tumor cell Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/05—Cyclic compounds having at least one ring containing boron but no carbon in the ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses a B (3)/B (3,6) -o-carborane alkylation method of a compound, which is characterized in that the compound is derived into active amide with an N-acyl-diimide group, and the active amide is cross-coupled with o-carborane with an imine group on a cage carbon under the catalysis of an Rh catalyst. The method can realize the carborane alkylation modification of functional compounds such as medicinal active substances, fluorescent molecules and the like, and can also carry out functionalization on the B (3)/B (3,6) position of o-carborane. Compared with the traditional coupling method, the invention realizes direct B-H activation functionalization, overcomes the defects of environmental pollution, dangerous reaction conditions, yield loss in multi-step reaction and the like caused by B (3) pre-activation in the prior art, and has better solubility and functional group compatibility and better industrial application prospect.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a B (3)/B (3,6) -o-carborane alkylation method of a compound.
Background
The carborane is polyhedral carborane molecular cluster, namely dodecahedral icosahedral dicarbo enclosed carborane (closo-C)2B10H12Hereinafter, abbreviated as "carborane"), there are three isomers, ortho carborane is widely used in luminescent materials, metal organic frameworks, nano-scale materials, electronic storage materials, liquid crystals, catalysis and other aspects due to its special properties such as three-dimensional aromaticity, large steric hindrance, multi-directional B-H and C-H bonds and non-classical interaction, and can be used as a good "mode molecule" for physical organic chemistry research. The o-carboranes have very high boronThe content of the boron has potential application in boron neutron capture therapy. Hosmane developed a water-soluble carbon nanotube modified with a large number of vicinal carborane groups, which utilized the properties of carbon nanotubes to highly aggregate boron-rich nested carboranes in a limited volume. The research shows that boron atoms can be enriched in blood and cancerated tissues of other organs, and the boron neutron capture therapy has very good application prospect for removing tumor tissues.
The orthocarbon borane has the characteristics of longer C-C bond, electron-withdrawing induction effect at the carbon end, electron-donating effect in different degrees at the boron end and the like, and the carborane has large steric hindrance effect and three-dimensional aromaticity, so that the distribution of electronic orbitals of HOMO and LUMO of a substituted compound can be adjusted, the whole boron cage can participate in electronic delocalization of adjacent luminous compound fragments, certain unusual regulation and control luminescence properties are displayed, and the orthocarbon borane can be applied to the regulation and control of the fluorescence activity property in a fluorescent molecule. For example, Lee research room in Korea and Yan hong professor group of subjects at Nanjing university summarize the rules of carborane group for fluorescence red shift, blue shift and quenching, and a part of molecules for regulating and controlling luminescence of carborane are found to be sensitive to dielectric constant of solvent, so that the carborane is applied to two-photon absorption and hypoxic imaging research of tumor cells.
Because two C-H of unsubstituted ortho-carborane molecules have strong acidity, and H of ten inert B-H bonds shows partial negative hydrogen property, the whole molecule has hydrophobicity and can form B-H … H-X hydrogen bonds, and the carborane is a very potential substituent group for drug molecules. Since 2010, Kagechika,
And
sufficient evidence for the presence of B-H-X (X ═ O, N, C) di-hydrogen bonds between the carborane groups and the proteins, respectively, was found. In 2015, Hawthorne and coworkers designed boron polycarbamine, which was the first B (3) -o-carboranyl tethered local anesthetic and was the only oneExample B (3) report of a biologically active orthocarborane derivative having an organic structure attached to the site.
To date, most carborane materials are compounds derivatized at the C-terminus. This is because the selective catalysis of the B-terminal has been very limited in the past, which also greatly affects the flexible selective attachment of carborane as a specific functional group to drug fragments and luminescent molecules. In the prior art, most carborane B (3) site selective substitution reactions require starting from a B (3) pre-functionalized precursor. Such a strategy requires multiple steps and presents risks (e.g. use of equivalent virulent TlOAc reagent, use of liquid ammonia, strong oxidant KMnO)4Neutralization of the remaining Na, THF at 110 ℃ for blocking reaction), moisture-sensitive reaction conditions (BI)3、PhBCl2The use of metallic Na) and low tolerance to functional groups.
Xu et al disclose an in-Situ Pd-NHC Catalytic System for regioselective Arylation of adjacent Carborane B (3,6) -H bond, synthesizing a series of symmetric and asymmetric 3, 6-diaryl-o-Carboranes (Old keys of The Lock in Carborane: The in Situ NHC-Palladium catalyst System for Selective aryl of B (3,6) -H Bonds of o-Carboranes via B-H activation. org. Lett.2019,21,9276 + 9279) with active groups. This method uses an excess of oxidant and the substrate type is limited by electron deficient substituents.
Tang et al, using a nucleophilic substitution strategy, propose a novel regioselective nucleophilic cage B-H substitution method for vicinal carboranes, leading to a series of dialkylated B (3,6) and alkylated/arylated vicinal carboranes. (Regioselective Nuclear amplification/Alkylation of B-H Bonds in o-carbohydrates: An Alternative Method for Selective vessel Boron functioning, J.Am.chem.Soc.2018, 140, 16423-16427).
However, the use of the Grignard reagent greatly limits the compatibility of functional groups (e.g., ester groups, amide groups, carbonyl groups, etc.) that are sensitive to the Grignard reagent. The reaction substrates available are limited. Lower reaction temperatures are detrimental to the dissolution of larger organic compounds, and thus it is difficult to achieve late stage boronation of complex organic compounds. In addition, the method must carry out reaction only by methyl and alkynyl which cannot be removed by C-terminal modification, otherwise, the reaction cannot be carried out.
At present, B (3) -o-carboranyl is linked to C (sp)2)/C(sp3) The organic substances present a great challenge because: (1) b (3) is the most electron deficient site in the cage structure. The electron enrichment order of the boron sites is: b (9,12)>B(8,10)>B(4,5,7,11)>B (3, 6). Thus, B (3) is easily attacked by nucleophiles, causing the boronization reaction to be a very serious disturbance in the chemical conversion of all compounds containing a closed-carboranyl group. Thus, many bases and even certain polar aprotic solvents cannot be used in order to avoid the deboronation reaction. In addition, boranes are reducing and oxidizing agents should be used with caution. For metal-induced electrophilic substitution, B (3) is more inert. (2) In most cases, it is necessary to pass through the carbon atom of the closure cage (i.e.C)cageReplacement of the H atom of-H with alkyl, aryl) to achieve selective B-H functionalization. To address the reactivity problem of electron deficient B (3) and B (4) ends, it is common to mount a Directing Group (DGs) at the carbon end of the carborane to force the reaction to occur at either B (3) or B (4). The existing studies show that C existscageIn the case of-H, mixtures of inseparable substitutions of B (3) and B (4) result. Furthermore, in most directed B-H activation reactions, which actually undergo electrophilic reaction mechanisms, coupled with the steric hindrance of the C-terminal placing group, the B (4) site is functionalized instead of the B (3) site. (3) The substrate applicability is narrow and at least one evaluation of the applicability to a wide range of synthetic chemistry is lacking. Although there are already some B (3)/B (4) -C (sp)2) Some reports have been coupled, but the generality of these methods has not been fully evaluated.
Disclosure of Invention
Aiming at the defects of the prior art, the invention discloses a B (3)/B (3,6) -o-carborane alkylation method, which uses o-carborane with imine mounted on cage carbon and sp derivative2Or sp3The active amide of hybridized carboxylic acid (as aryl source, alkenyl source and alkyl source) is catalyzed by Rh (I) to realize B (3) -o-carbon alkyl and C (sp)2)/C(sp3) Cross-coupling of (3).
The specific technical scheme of the invention is as follows:
a process for the B (3)/B (3,6) -o-carborane alkylation of compounds characterized by derivatizing the compounds into activated amides having N-acyl-imide groups, cross-coupling with an o-carborane having an imine group on a cage carbon, catalyzed by Rh catalyst.
Preferably, the Rh catalyst is selected from [ Rh (cod) Cl]2And/or Rh2(CO)4Cl2。
In the method of the present invention, the N-acyl-imide group has the following parent nucleus structure:
n is an integer of 0 to 5. When n represents 1 to 5, the parent nucleus may have one or more of the same or different substituents, such as C1-10 alkyl, C1-10 alkoxy, C1-10 ester group, halogen group and the like. Preferably, the N-acyl-imide group is a substituted or unsubstituted N-acyl-glutarimide or N-acyl-succinimide.
According to the method, the nitrogen atom on the imine group on the adjacent carborane cage carbon is substituted by aryl or heteroaryl. Further, the aryl or heteroaryl group is a substituted or unsubstituted phenyl group, a substituted or unsubstituted bicyclic or tricyclic aromatic group, (e.g., naphthyl group, anthracenyl group substituted with H, C1-10 alkyl group, C1-10 alkoxy group, C1-10 ester group, halogen group, etc.) or a substituted or unsubstituted monocyclic, bicyclic or tricyclic heterocyclic aromatic group containing one or more N, O, S hetero atoms (e.g., furyl group, thienyl group, pyrrolyl group, thiazolyl group, imidazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolyl group, quinolyl group, pteridinyl group, acridinyl group, etc., substituted with H, C1-10 alkyl group, C1-10 alkoxy group, C1-10 ester group, halogen group, etc.). Preferably phenyl, thienyl, furyl, pyridyl and pyrimidyl which are substituted by one or more of H, methyl, ethyl, propyl, isopropyl, butyl and tert-butyl.
In a specific embodiment of the invention, aryl is selected from
(Mes)。
The orthocarborane having an imine group has the following structure:
ar represents an aryl or heteroaryl group, R1Represents H or C1-C10 alkyl.
Specifically, the method is characterized by comprising the following reaction formula:
R1represents H, C1-C10 alkyl, R2，R3And represents the residue of the compound to be alkylated by B (3)/B (3,6) -o-carborane in the invention, Ar is defined as the above, and represents substituted or unsubstituted phenyl, monocyclic, bicyclic or tricyclic aromatic group or monocyclic, bicyclic or tricyclic heterocyclic aromatic group containing one or more N, O, S heteroatoms, n is an integer of 1-5, preferably n is 2 or 3.
Preferably, R2、R3Represents phenyl, biphenyl, naphthyl, pyridyl, oxazinyl, thiophene, phenyl substituted at any position by one or more of H, C1-C8 alkyl, C3-C8 cycloalkyl, C1-C8 alkoxy, C1-C8 haloalkyl, C1-C8 ester, aldehyde, halogen, cyano, amine, carbonyl, amide, sulfone, sulfoxide, thio, sulfonamide, nitro, phosphonyl, trifluoromethyl, trifluoromethoxy, thifluoromethyl, alkenyl, fluoroalkyl, polyfluoroaryl, aryl, glycosyl, purinyl, pyrimidinyl, carboranylA group selected from the group consisting of a furyl group, a thiazolyl group, an oxazolyl group, and an imidazolyl group.
In a specific example of the present invention, R2、R3Represents:
in the method, the preferable reaction temperature is 130-150 ℃, and the reaction solvent is one or more selected from toluene, o-xylene, m-xylene or p-xylene.
When carboxyl or acyl chloride or acyl bromide groups in the structure of the compound are in reaction, the compound can directly react with diimide to obtain active amide with N-acyl-diimide groups, or the compound is converted through derivatization reaction and then is connected with the carboxyl or acyl chloride or acyl bromide groups to react with the diimide.
The method of the invention also comprises the step of further converting the obtained B (3)/B (3,6) -o-carborane alkylate after the reaction is finished.
The conversion comprises one or more of removal of an imine group on an o-carborane caged carbon, stitution of a substituted carbon end of carborane, boronization of carborane or derivatization of a compound residue part, and the like.
In the method of the present invention, when an active hydrogen group is present in the compound, it is preferable that the active hydrogen group is protected with a protecting group before the reaction, and the protecting group is removed after cross-coupling with an o-carborane having an imine group on a cage carbon. The active hydrogen group is selected from one or more of hydroxyl, amino, sulfydryl, carboxyl, sulfo and sulfonamido. The protecting group may be a conventionally used protecting group such as BHT (2, 6-di-t-butyl-4-methylphenyl), Bn (benzyl), BOC (t-butyloxycarbonyl), BOM (benzyloxymethyl), Cbz (benzyloxycarbonyl), CDA (cyclohexyl-1, 2-diketal), DAN (dansyl), Fmoc (9-fluorenylmethoxycarbonyl), TBDMS (t-butyldimethylsilyl).
The invention has the advantages that:
the invention successfully introduces compound fragments into the B (3)/B (3,6) position of o-carborane by derivatizing a compound into an active amide with an N-acyl-diimide group and carrying out cross coupling with o-carborane with an imine group on a cage carbon under the catalysis of Rh (I). The method can realize the carborane alkylation modification of functional compounds such as medicinal active substances, fluorescent molecules and the like, and can also carry out functionalization on the B (3)/B (3,6) position of o-carborane.
The invention uses N-acyl-diimide active amide as the precursor of compound fragment with aryl, heteroaryl, alkenyl, primary alkyl, etc. and uses Rh (I) to perform two-step oxidation addition to the primary amido bond of B-H bond, so that no oxidant is needed in the reaction. In addition, because amine-based anions are generated in the reaction process, no additional strong alkaline substances are needed for the reaction. This allows the carborane cage to be protected from oxidation and decomposition by the presence of strong bases.
Compared with the traditional coupling method, the method realizes direct B-H activation functionalization, and avoids environmental pollution, dangerous reaction conditions and yield loss in multi-step reaction caused by B (3) preactivation. Compared with the reported B (3) -H activation functionalization method, the reaction uses the toluene reflux condition, and compared with the reported normal-temperature B (3) -H functionalization, the reaction has better solubility and functional group compatibility by taking toluene as a solvent at high temperature. The method can be used for realizing the connection of the C (sp2) or C (sp3) synthetic building block and the carborane B (3) or B (3,6) site. Because the amide substrate in the invention is derived from a corresponding carboxylic acid substrate and is easy to store, the reaction substrate has a wide range and is extremely suitable for late-stage carborane alkylation modification of organic compounds. The reactive amidation of N-acyl-diimides of compounds avoids the formation of B-X (X ═ I, Br, Cl), B-O bonds containing by-products resulting from derivatization of the compounds to halogenated aromatic hydrocarbons, halogenated olefins, halogenated alkanes substrates and possible additives. In addition, the method can be carried out in an enlarged scale, and has a good industrial application prospect.
Detailed Description
The following examples illustrate specific steps of the present invention, but are not intended to limit the invention.
Terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art, unless otherwise specified.
The present invention is described in further detail below with reference to specific examples and with reference to the data. It will be understood that these examples are intended to illustrate the invention and are not intended to limit the scope of the invention in any way.
In the following examples, various procedures and methods not described in detail are conventional methods well known in the art.
Example 1 screening of reaction conditions
According to the conditions shown in Table 1, compound 40(1- [ (1E) -2- (2,4,6-trimethylphenylethenyl) ] -1, 2-dicarbadecaborane, 58.2mg,0.2mmol), active amide (a, b, c, d or E) (0.44mmol), rhodium catalyst (0.01mmol) was added to a dried 10mL Schlenk tube and purged with argon three times. After toluene (1.0mL) was added, the tube was closed. After 24 hours the tube was cooled to room temperature and filtered using 2 cm of celite under a rinse of ethyl acetate. The celite was rinsed with DCM (2X 5 mL). The collected organic solvents were dried and separated by Preparative TLC (PTLC) to give mono-and di-substituents (mono) and (di).
Mes stands for
TABLE 1
The results show that Compound 40 and active amide a are present under standard conditions (5 mol%, [ Rh (cod) Cl)]2Stirred in toluene at 150 ℃ for 24 hours) the product was obtained in 93% isolated yield (mono-: di-11: 82, example 1). Using Rh2(CO)4Cl2The catalyst gave the product (mono-: di-20:58, example 2). After switching to the other rhodium catalyst, no desired product was detected (examples 3 to 7). When activated amide b was used, the overall yield dropped to 73% (example 8). When the other three active amides c-e were studied, no product was obtained (examples 9-11). Whereas only traces of product were detected when the temperature was reduced to 100 ℃ (example 10).
Example 2
Preparation of activated amides having N-acyl-diimide groups
the following examples may be used for preparation
Scheme A:
scheme B:
scheme C:
the moiety of the compound having an N-acyl-imide group is selected from the group consisting of:
(2) preparation of mono-/di-carborane alkylated compounds
With reference to the method of example 1, the optimum reaction conditions were selected, and the activated amide obtained in step (1) was cross-coupled with compound 40 to examine the utility of the carborylation (B (3) vertex) reaction under the optimum conditions.
The results show that N-acyl-glutarimides with Electron Donating Groups (EDG) or Electron Withdrawing Groups (EWG) in the para position react smoothly (groups 2-14), while compounds with EWG have better yields (groups 5-18). Methoxy (group 2), 2,4,6-trimethylphenyl (group 3), alkenyl (group 4), pentafluorophenyl (group 5), fluoro (group 6), nitrile (group 7), trifluoromethyl (group 8), oxytrifluoromethyl (group 9), chloride (group 10), bromide (group 11), phosphonyl (group 12), ketone (group 13), C-o-boryl (group 14) are well tolerated (yield up to 95%). After finding the yield reduction due to the para-methoxy group, the present invention installs several EDGs in meta position of N-acyl-glutarimide and finally obtains high yield of the compound (groups 15-17). Large sterically hindered groups, such as cyclohexyl and methyl, hinder the formation of compounds (groups 18 and 19), while less hindered fluorides (group 20) have good yields. The conversion of naphthalene containing substrates (group 21) requires 10 mol% catalyst loading and, in addition, electron rich heteroarylthienyl (group 22), furyl (group 23) or electron deficient pyridyl (group 24) perform well in cross-coupling with B (3) -o-carboranyl under optimized conditions. The yield of less sterically hindered linear alkenyl substrates (groups 25 and 27) is higher. Under the same conditions, the alkyl substrates can also undergo ortho-carborylation (at the B (3) position) in moderate yields (28-30). Molecules containing coordinating atoms such as oxygen and nitrogen can also be readily converted to the corresponding B (3) -o-carboranyl-C (sp2) coupling product (groups 31-39). It has been shown that complex steroid derivatives are excellent couplers, and that the ketone function (group 36), which is extremely sensitive during the coupling process, is not disturbed. The general amide bond is not cleaved under the conditions of the present invention (group 34), demonstrating the ideal selectivity and utility of the process.
All compounds were synthesized as follows unless otherwise specified. Compound 40(58.2mg,0.2mmol), activated amide (0.4)4mmol for sp2Hybridized amides use N-acyl-glutarimides for sp2The hybridized amide uses N-acyl-succinimide), [ Rh (cod) Cl]2(5.6mg,0.01mmol) was added to a 10mL oven dried Schlenk tube, which was then evacuated three times and placed under Ar. Toluene (1.0mL) was added, the tube was sealed and stirred at 150 ℃. After 24 hours, the tube was cooled to room temperature and filtered using 2 cm of celite under a rinse of ethyl acetate. The celite was rinsed with DCM (2X 5 mL). The collected organic solvent was spun dry and separated by preparative tlc (ptlc) to give the product.
Note that for the synthesis of the compounds (groups 21 and 33), [ Rh (cod) Cl needs to be used]2(11.2mg,0.02mmol)。
The structure identification results are shown below:
1：
(yield 93%, mono: di 11: 82).
mono：1H NMR(400MHz,CDCl3):7.61(d,J＝7.1Hz,2H),7.42–7.29(m,4H),6.71(s,2H),4.70(s,1H),2.19(s,3H),1.51(s,6H)。
11B{H}NMR(125MHz,CDCl3):-2.2,-3.1,-8.2,-11.5,-13.9。
13C NMR(100MHz,CDCl3):155.0,144.8,134.5,134.4,129.9,128.8,128.4,126.9,73.8,55.8,20.6,17.3。
di：1H NMR(400MHz,CDCl3):7.67–7.63(m,4H),7.40–7.29(m,6H),7.23(s,1H),6.56(s,2H),4.85(s,1H),2.11(s,3H),1.01(s,6H)。
11B{1H}NMR(125MHz,CDCl3):0.2,-1.4,-4.3,-10.5,-12.6。
13C NMR(100MHz,CDCl3):153.0,144.6,134.5,134.4,129.8,128.7,127.6,74.7,54.2,20.5,16.7。
2：
(yield 62%, mono: di 30: 32).
mono：1H NMR(400MHz,CDCl3):7.52(d,J＝8.6Hz,2H),7.39(s,1H),6.87(d,J＝8.6Hz,2H),6.72(s,2H),4.66(s,1H),3.81(s,3H),2.20(s,3H),1.55(s,6H)。
11B{1H}NMR(125MHz,CDCl3):-2.3,-3.3,-8.2,-12.0,-13.8。
13C NMR(100MHz,CDCl3):161.2,155.1,144.9,135.8,134.5,128.8,126.9,114.0,73.7,55.8,55.2,20.6,17.3。
di：1H NMR(400MHz,CDCl3):7.56(d,J＝8.3Hz,4H),7.22(s,1H),6.86(d,J＝8.5Hz,4H),6.59(s,2H),4.77(s,1H),3.81(s,6H),2.14(s,3H),1.10(s,6H)。
11B{1H}NMR(125MHz,CDCl3):5.8,3.9,0.4,-5.6,-7.4。
13C NMR(100MHz,CDCl3):161.2,153.4,144.8,136.0,134.4,128.7,127.6,113.9,74.5,55.2,54.2,20.6,16.7。
3：
(yield 39%, mono: di: 14: 25).
4：
(yield 25%, mono: di 10: 15).
5：
(yield 55%, mono: di 10: 45).
6：
(yield 91%, mono: di 10: 80).
7：
(yield 74%, mono: di: 19: 55).
8：
(yield 95%, mono: di 15: 80).
9：
(yield 83%, mono: di: 12: 71).
10：
(yield 79%, mono: di 25: 54).
11：
(yield 63%, mono: di 25: 38).
12：
(yield 58%).
13：
(yield 68%, mono: di 15: 53).
14：
(yield 58%, mono: di: 34: 24).
mono：1H NMR(400MHz,CDCl3):7.82–7.54(m,4H),7.40(s,1H),6.71(s,2H),4.72(s,1H),2.18(s,3H),1.72(s,3H),1.48(s,6H)。
11B{1H}NMR(125MHz,CDCl3):-2.4,-4.5,-9.2,-9.9,-13.6,-14.8。
13C NMR(100MHz,CDCl3):154.6,144.5,134.9,134.8,132.5,130.8,129.0,126.6,81.3,73.8,60.4,55.4,23.3,20.6,17.4。
di：1H NMR(400MHz,CDCl3):7.69–7.52(m,8H),7.23(s,1H),6.55(s,2H),4.86(s,1H),2.11(s,3H),1.66(s,6H),0.94(s,6H)。
11B{1H}NMR(125MHz,CDCl3):-0.8,-2.6,-4.6,-10.1。
13C NMR(100MHz,CDCl3):152.1,143.6,135.3,135.0,132.6,130.7,129.0,127.2,81.3,74.7,54.0,23.2,20.5,17.2,16.8。
15：
(yield 83%, mono: di: 36: 47).
16：
(yield 75%, mono: di 35: 45).
17：
(yield 73%, mono: di: 21: 52).
18：
(yield 30%).
1H NMR(400MHz,CDCl3):7.48(d,J＝7.6Hz,2H),7.36–7.30(m,4H),7.18(s,1H),7.10(ddd,J＝7.7,6.2,2.4Hz,2H),6.50(s,2H),5.04(s,1H),2.08(s,3H),1.90–1.30(m,22H),0.88(s,6H)
11B{1H}NMR(125MHz,CDCl3):-2.2,-4.3,-13.3,-13.8。
13C NMR(100MHz,CDCl3):154.6,154.0,135.4,134.0,130.2,128.6,128.5,127.5,127.2,125.5,54.5,40.9,34.9,34.7,26.9,26.1,20.5,16.6。
19：
(yield 41%, mono: di 20: 21).
20：
(yield 77%, mono: di 23: 54).
21：
(yield 76%, mono: di 20: 56).
22：
(yield 90%, mono: di: 18: 72).
mono：1H NMR(400MHz,CDCl3):7.49(dd,J＝4.8,1.0Hz,1H),7.46(s,1H),7.34(dd,J＝3.4,1.0Hz,1H),7.09(dd,J＝4.9,3.4Hz,1H),6.47(s,2H),4.69(s,1H),2.21(s,3H),1.62(s,6H)。
11B{1H}NMR(125MHz,CDCl3):-1.3,-4.4,-10.2,-12.3。
13C NMR(100MHz,CDCl3):154.8,144.7,135.7,134.7,131.1,128.9,128.6,127.0,73.8,57.2,20.6,17.2。
di：1H NMR(400MHz,CDCl3):7.49(dd,J＝4.8,1.0Hz,2H),7.37(dd,J＝3.4,1.0Hz,2H),7.35(s,1H),7.08(dd,J＝4.8,3.4Hz,2H),6.66(s,2H),4.86(s,1H),2.17(s,3H),1.28(s,6H)。
11B{1H}NMR(125MHz,CDCl3):-1.7,-4.5,-10.3,-12.4。
13C NMR(100MHz,CDCl3):152.0,144.2,136.0,134.8,131.2,128.9,128.4,128.0,74.4,56.4,20.6,16.7。
23：
(yield 82%, mono: di 22: 60).
mono：1H NMR(400MHz,CDCl3):7.51(d,J＝1.7Hz,1H),7.48(s,1H),6.82(d,J＝3.3Hz,1H),6.77(s,2H),6.38(dd,J＝3.3,1.7Hz,1H),4.73(s,1H),2.22(s,3H),1.73(s,6H)。
11B{1H}NMR(125MHz,CDCl3):-2.2,-3.1,-4.7,-6.4,-8.1,-10.6,-11.9,-13.0。
13C NMR(100MHz,CDCl3):154.8,146.4,134.6,129.1,128.9,126.9,120.8,110.8,73.6,56.8,20.7,17.5。
di：1H NMR(400MHz,CDCl3):7.50(s,2H),7.37(d,J＝1.5Hz,1H),6.86(d,J＝3.2Hz,2H),6.70(s,2H),6.38(dd,J＝3.2,1.7Hz,2H),4.89(s,1H),2.19(s,3H),1.50(s,6H)。
11B{1H}NMR(125MHz,CDCl3):3.8,0.3,-4.6,-6.5,-7.6。
13C NMR(100MHz,CDCl3):152.9,146.2,134.5,128.8,128.0,127.4,121.0,110.9,74.4,56.2,20.6,17.1。
24：
(yield 83%, mono: di: 36: 47).
mono：1H NMR(400MHz,CDCl3):8.36(dd,J＝2.2Hz,0.8Hz,1H),7.73(dd,J＝8.4Hz,2.2Hz,1H),7.40(s,1H),6.72(s,2H),6.70(d,J＝0.8Hz,1H),4.67(s,1H),3.92(s,3H),2.19(s,3H),1.57(s,6H)。
11B{1H}NMR(125MHz,CDCl3):-1.9,-3.0,-7.9,-11.3,-13.6。
13C NMR(100MHz,CDCl3):186.6,166.9,154.8,152.6,143.9,134.7,128.9,126.7,110.9,74.2,55.3,53.5,20.6,17.4。
di：1H NMR(400MHz,CDCl3):8.38(dd,J＝2.2,0.8,2H),7.73(dd,J＝8.4Hz,2.2Hz,2H),7.25(s,1H),6.68(dd,J＝8.5Hz,0.7Hz,2H),6.60(s,2H),4.77(s,1H),3.91(s,6H),2.12(s,3H),1.13(s,6H)。
11B{1H}NMR(125MHz,CDCl3):-0.3,-3.8,-10.2,-12.4。
13C NMR(100MHz,CDCl3):165.3,152.8,144.2,144.0,134.9,129.2,129.0,127.4,110.8,74.2,53.9,53.6,20.5,16.9。
25：
(yield 96%, mono: di: 16: 80).
mono：1H NMR(400MHz,CDCl3):7.46(s,1H),7.32(d,J＝7.4Hz,2H),7.28–7.17(m,
3H)7.09(d,J＝18.1Hz,1H),6.71(s,2H),6.20(d,J＝18.1Hz,1H),4.41(s,1H),2.14(s,3H),1.86(s,6H)。
11B{1H}NMR(125MHz,CDCl3):2.9,2.4,-3.4,-4.0,-6.6,-8.4,-9.6。
13C NMR(100MHz,CDCl3):155.5,147.4,145.0,137.1,134.7,129.0,128.8,128.6,126.8,126.6,118.3,72.8,56.3,20.6,18.2。
di：1H NMR(400MHz,CDCl3):7.41(s,1H),7.30(d,J＝8.0Hz,4H),7.27–7.15(m,6H),7.11(d,J＝18.1Hz,2H),6.66(s,2H),6.23(d,J＝18.2Hz,2H),4.33(s,1H),2.10(s,3H),1.83(s,6H)。
11B{1H}NMR(125MHz,CDCl3):3.0,0.8,-6.2。
13C NMR(100MHz,CDCl3):154.4,147.2,145.0,137.2,134.8,129.2,128.64,128.57,127.4,126.6,119.1,73.0,56.5,20.6,18.3。
26：
(yield 47%).
27：
(yield 84%, mono: di-18: 66).
28：
(yield 62%, mono: di 23: 39).
mono：1H NMR(400MHz,CDCl3):7.60(s,1H),7.31–7.26(m,2H),7.22–7.18(m,3H),6.86(s,2H),4.34(s,1H),2.95–2.89(m,2H),2.28(s,3H),2.05(s,6H),1.47–1.41(m,2H)。
11B{1H}NMR(125MHz,CDCl3):-1.0,-2.8,-9.0,-12.2。
13C NMR(100MHz,CDCl3):155.5,144.8,143.3,135.0,129.3,128.4,127.8,127.0,125.9,73.0,57.0,33.9,20.7,18.5,16.0(br)。
di：1H NMR(400MHz,CDCl3):7.57(s,1H),7.29–7.23(m,4H),7.20–7.14(m,6H),6.88(s,2H),4.07(s,1H),2.96–2.83(m,4H),2.28(s,3H),2.12(s,6H),1.42–1.38(m,4H)。
11B{1H}NMR(125MHz,CDCl3):0.03,-2.7,-3.5,-12.0。
13C NMR(100MHz,CDCl3):154.0,144.1,143.5,135.6,129.7,129.3,128.4,128.1,127.8,125.8,73.5,58.1,34.0,20.7,18.9,16.8(br)。
29：
(yield 56%).
1H NMR(400MHz,CDCl3):7.82(dd,J＝5.4Hz,3.0Hz,2H),7.70(dd,J＝5.5Hz,3.0Hz,2H),7.59(s,1H),6.80(s,2H),4.40(s,1H),3.95(dd,J＝9.5Hz,7.3Hz,2H),2.23(s,3H),2.01(s,6H),1.55–1.51(m,2H)。
11B{1H}NMR(125MHz,CDCl3):2.7,-3.7,-6.7。
13C NMR(100MHz,CDCl3):168.1,155.0,135.0,133.9,132.0,129.2,127.0,123.2,73.1,57.2,36.7,20.6,18.4,14.4(br)。
HRMS m/z(ESI):calcd for C22H30B10N2O2(M+H)+,465.3316,found。
30：
(yield 51%).
1H NMR(400MHz,CDCl3):7.55(s,1H),6.86(s,2H),5.77(m,1H),5.04–4.89(m,2H),4.25(s,1H),2.26(s,3H),2.11(m,2H),2.05(s,6H),1.67–1.63(m,2H),1.08–0.99(m,2H)。
11B{1H}NMR(125MHz,CDCl3):-0.7,-2.9,-9.1,-12.5。
13C NMR(100MHz,CDCl3):155.7,138.3,134.9,129.2,126.9,115.1,72.9,57.0,36.3,27.5,20.7,18.5,14.0(br)。
31：
(yield 54%, mono: di: 21: 33).
32：
(yield 56%, mono: di: 32: 24).
33：
(yield 39%).
1H NMR(400MHz,CDCl3):8.39(s,1H),8.21(d,J＝7.7Hz,1H),7.78(t,J＝7.8Hz,1H),7.67(s,1H),7.45(s,1H),7.43(d,J＝8.1Hz,1H),6.65(s,2H),4.85(s,1H),2.45(s,3H),2.43(s,3H),2.13(s,3H),1.53(s,6H)。
11B{1H}NMR(125MHz,CDCl3):2.9,-2.7,-4.3,-5.7,-6.8,8.0。
13C NMR(100MHz,CDCl3):181.7,180.6,169.4,169.0,154.2,153.1,151.0,150.0,149.7,144.4,135.6,134.8,134.2,133.6,130.6,130.5,128.9,126.6,126.1,125.6,74.1,55.6,21.0,20.6,18.1,17.5。
34：
(yield 78%, mono: di 32: 46).
mono：1H NMR(500MHz,CDCl3):8.04(dd,J＝4.9Hz,2.0Hz,1H),7.84(dt,J＝7.6Hz,1.6Hz,1H),7.54–7.46(m,4H),7.37(s,1H),7.30(d,J＝7.7Hz,2H),7.17–7.07(m,2H),7.00(dd,J＝7.5Hz,4.9Hz,1H),6.95(s,1H),6.72–6.64(m,3H),6.60(s,1H),5.40(d,J＝15.1Hz,1H),4.71(d,J＝15.7Hz,1H),4.67(s,1H),2.19(s,3H),1.48(s,6H)。
11B{1H}NMR(156MHz,CDCl3):2.49,-2.86,-6.47,-7.83。
13C NMR(125MHz,CDCl3):167.2,162.0(dd,J＝252.3Hz,11.4Hz),157.7(dd,J＝253.1Hz,12.4Hz),157.3,154.7,153.0,148.5,144.6,138.9,138.2,134.7,134.6,131.8(q,J＝32.8Hz),131.0(d,J＝9.7Hz),130.0,129.1,128.8,126.8,125.5(dd,J＝12.2Hz,4.0Hz),124.65,124.59,121.7(q,J＝3.5Hz),120.8,118.8,118.3(q,J＝3.7Hz),111.5(dd,J＝22.3Hz,3.4Hz),104.9(t,J＝25.4Hz),73.7,55.6,52.2,20.6,17.2,
19F NMR(376MHz,CDCl3):-62.2(s,3F),-107.4(s,1F),-113.7(s,1F)。
di：1H NMR(500MHz,CDCl3):8.13(dd,J＝4.9Hz,1.7Hz,2H),7.91(d,J＝7.4,2H),7.65–7.56(m,8H),7.40–7.30(m,5H),7.21(s,4H),7.09(dd,J＝7.4Hz,5.0Hz,2H),6.99–6.92(m,2H),6.72(s,2H),6.61–6.58(m,4H),5.49(d,J＝15.4Hz,2H),4.85(s,1H),4.76(d,J＝14.9Hz,2H),2.20(s,3H),1.06(s,6H)。
11B{1H}NMR(156MHz,CDCl3):-1.7,-4.0,-12.7。
13C NMR(125MHz,CDCl3):167.2,161.9(dd,J＝252.2Hz,11.3Hz),157.7(dd,J＝253.1Hz,12.3Hz),157.3,153.1,152.8,148.6,144.2,138.9,138.0,134.7,134.6,131.8(q,J＝32.7Hz),131.0(q,J＝6.7Hz),130.1,128.7,128.0(d,J＝10.9Hz),127.5,125.4(dd,J＝12.2Hz,3.8Hz),124.6,123.6(q,J＝272.4Hz),121.6(q,J＝3.5Hz),120.9,118.8,118.3(q,J＝3.6Hz),111.5(d,J＝22.1Hz),104.9(t,J＝25.0Hz),74.5,54.4,52.1,20.4,16.8。
19F NMR(376MHz,CDCl3):-62.1(s,6F),-107.5(s,2F),-113.7(s,2F)。
35：
(yield 63%, mono: di 45: 18).
mono：1H NMR(400MHz,CDCl3):7.53(d,J＝8.5Hz,2H),7.37(s,1H),6.94(d,J＝8.0Hz,2H),6.70(s,2H),5.37–5.23(m,2H),5.17(td,J＝9.4Hz,2.8Hz,1H),5.06(dd,J＝7.5Hz,2.2Hz,1H),4.65(s,1H),4.29(ddd,J＝12.3Hz,5.4Hz,3.6Hz,1H),4.15(ddd,J＝12.4Hz,5.5Hz,2.5Hz,1H),3.85(ddd,J＝10.1Hz,5.3Hz,2.5Hz,1H),2.18(s,3H),2.09–1.96(m,12H),1.53(s,3H),1.52(s,3H)。
11B{1H}NMR(125MHz,CDCl3):-2.6,-8.3,-13.1。
13C NMR(100MHz,CDCl3):170.5,170.3,169.4,169.3,158.4,154.9,144.7,135.9,134.7,128.9,126.8,116.7,98.7,74.4,73.8,72.6,72.1,71.1,68.2,61.9,57.2,55.6,20.6,17.8,17.32,17.29。
di：1H NMR(400MHz,CDCl3):7.54(d,J＝8.6Hz,4H),7.18(s,1H),6.91(d,J＝7.3Hz,4H),6.55(s,2H),5.35–5.21(m,4H),5.15(td,J＝9.6Hz,1.3Hz,2H),5.05(dd,J＝7.4Hz,3.0Hz,2H),4.75(s,1H),4.27(dd,J＝12.3Hz,5.2Hz,2H),4.12(ddd,J＝12.0Hz,3.7Hz,2.3Hz,2H),3.83(ddd,J＝10.0Hz,5.2Hz,2.4Hz,2H),2.11(s,3H),2.06–2.00(m,24H),1.02(s,6H)。
11B{1H}NMR(125MHz,CDCl3):-0.6,-4.0,-11.7。
13C NMR(100MHz,CDCl3):170.44,170.42,170.2,169.3,169.2,158.3,152.9,144.3,140.0,134.7,128.8,127.4,116.6,98.7,98.6,74.4,72.5,72.0,71.0,68.2,61.8,54.1,20.54,20.53,20.4,16.6。
36：
(yield 72%, mono: di: 42: 30).
mono：1H NMR(400MHz,CDCl3):7.61(d,J＝8.2Hz,2H),7.42–7.34(m,3H),7.20(d,J＝8.6Hz,1H),6.77(d,J＝2.9Hz,1H),6.72(d,J＝2.8Hz,1H),6.69(s,2H),5.04(s,2H),4.69(s,1H),2.90(dd,J＝8.0Hz,5.0Hz,2H),2.51(dd,J＝18.8Hz,8.6Hz,1H),2.44–2.37(m,1H),2.27(td,J＝10.5Hz,3.9Hz,1H),2.22–1.92(m,7H,4H from Estrone and 3H from Mes),1.37–1.07(m,12H,6H from Estrone and 6H from Mes),0.91(s,3H)。
11B{1H}NMR(125MHz,CDCl3):-2.6,-8.2,-9.2,-11.7,-13.7。
13C NMR(100MHz,CDCl3):221.0,156.6,155.0,144.8,139.4,137.9,134.6,134.3,132.4,128.8,127.1,126.9,126.4,114.9,112.3,73.8,69.3,55.7,50.4,48.0,44.0,38.4,35.9,31.6,29.7,26.6,26.0,21.6,20.7,17.4,13.9。
di：1H NMR(400MHz,CDCl3):7.63(d,J＝8.0Hz,4H),7.36(d,J＝7.8Hz,4H),7.20(m,3H),6.80–6.66(m,4H),6.51(s,2H),5.02(s,1H),2.88(dd,J＝7.1Hz,3.5Hz,4H),2.51(dd,J＝18.8Hz,8.5Hz,2H),2.43–2.36(m,2H),2.30–2.22(m,2H),2.21–1.93(m,12H),1.70–1.36(m,12H),1.26(s,3H),0.95(s,6H),0.90(s,6H)。
11B{1H}NMR(125MHz,CDCl3):；-0.6,-10.4。
13C NMR(100MHz,CDCl3):220.9,156.6,153.0,144.6,139.2,137.8,134.7,134.3,132.4,128.7,127.5,126.9,126.3,114.9,112.3,74.6,69.3,54.1,50.4,48.0,44.0,38.3,35.8,31.6,29.6,26.5,25.9,21.6,20.5,16.7,13.8。
37：
(yield 37-91%).
1H NMR(400MHz,CDCl3):7.64(d,J＝7.3Hz,4H),7.59(d,J＝7.9Hz,2H),7.33–7.28(m,3H),7.26–7.11(m,4H),6.77(d,J＝8.8Hz,2H),6.57(s,2H),6.27(d,J＝18.2Hz,1H),5.01(hept,J＝6.2Hz,1H),4.62(s,1H),2.07(s,3H),1.59(s,6H),1.41(s,6H),1.14(s,3H),1.12(s,3H)。
11B{1H}NMR(125MHz,CDCl3):-2.0,-11.7。
13C NMR(100MHz,CDCl3):194.9,173.1,159.7,153.5,147.4,144.6,139.2,137.2,134.9,134.4,132.0,130.2,129.2,129.1,128.8,128.6,127.4,126.7,117.2,79.4,73.9,69.4,55.5,30.9,25.42,25.37,21.6,20.6,17.7.
HRMS m/z(ESI):calcd for C40H49B10NO4(M+H)+718.4670,found 718.4674。
38：
(yield 38-63%).
1H NMR(500MHz,CDCl3):7.57(d,J＝8.1Hz,2H),7.36(d,J＝7.1Hz,3H),7.17(s,1H),7.06(s,1H),6.85(s,1H),6.69(s,2H),5.15(s,1H),3.81(s,3H),3.71(s,3H),3.67(s,2H),2.50(s,3H),2.17(s,3H),1.50(s,6H)。
11B{1H}NMR(156MHz,CDCl3):-3.3,-8.2,-12.2。
13C NMR(125MHz,CDCl3):171.1,188.1,159.0,155.7,145.2,139.4,137.5,134.3,133.8,132.3,130.92,130.86,129.2,128.7,126.6,123.9,112.2,99.4,73.7,57.0,55.6,52.2,30.1,20.6,17.2,13.2。
HRMS m/z(ESI):calcd for C32H40B10ClN2O4(M+H)+661.3607,found 661.3600。
39：
(yield 39-87%).
1H NMR(400MHz,CDCl3):7.69(d,J＝7.8Hz,2H),7.56(dd,J＝10.3,7.4Hz,4H),7.33–7.17(m,4H),6.85(d,J＝2.5Hz,1H),6.74(d,J＝9.0Hz,1H),6.51(s,2H),6.35(dd,J＝9.0,2.6Hz,1H),4.79(s,1H),3.73(s,3H),3.62(s,3H),3.57(s,2H),2.24(s,3H),2.04(s,3H),1.06(s,6H)。
11B{1H}NMR(125MHz,CDCl3):-0.9,-11.8。
13C NMR(100MHz,CDCl3):171.4,168.8,156.0,152.6,144.1,136.5,136.0,134.9,134.8,134.5,130.8,130.6,130.0,129.2,129.0,128.3,127.6,115.0,112.3,111.3,101.4,78.6,74.7,55.7,54.6,52.2,30.2,20.5,17.1,13.4.
HRMS m/z(ESI):calcd for C38H45B10N2O4(M+H)+703.4310,found 703.4316。
Example 5 further conversion of B (3)/B (3,6) -o-carborane alkylate
(1) In the case of compound 1, gram-weight synthesis was performed
Compound 40(1000.0mg,3.44mmol), active amide a (1650.0mg,7.57mmol), [ Rh (cod) Cl, were added to a 200mL sealable Schlenk tube as previously described]2(96.3mg,0.17 mmol). The atmosphere was changed to Ar by pumping three times, and 17mL of toluene was added. Column chromatography gave 1-mono (185.6mg,0.52mmol, 15%) and 1-di (1141.9mg,2.61mmol, 76%).
Claims (10)
1. A process for the B (3)/B (3,6) -o-carborane alkylation of compounds characterized by derivatizing the compounds into activated amides having N-acyl-imide groups in the presence of an Rh catalyst [ Rh (cod) Cl]2And/or Rh2(CO)4Cl2Catalytically cross-coupling with an o-carborane having an imine group on a cage carbon, wherein the N-acyl-diimide group has the following parent-nucleus structure:
n is an integer of 1 to 5.
2. A method according to claim 1, wherein the N-acyl-imide group is a substituted or unsubstituted N-acyl-glutarimide or N-acyl-succinimide.
3. A process according to claim 1, wherein the nitrogen atom of the imine group on the carbon of the o-carborane cage is substituted with an aryl or heteroaryl group, said aryl or heteroaryl group being a substituted or unsubstituted phenyl group, a substituted or unsubstituted bicyclic or tricyclic aromatic group, or a substituted or unsubstituted monocyclic, bicyclic or tricyclic heteroaromatic group containing one or more heteroatoms of N, O, S.
4. A method according to claim 3, wherein the aryl or heteroaryl group is selected from the group consisting of substituted or unsubstituted phenyl, naphthyl, anthracenyl, furyl, thienyl, pyrrolyl, thiazolyl, imidazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, quinolinyl, pteridinyl, acridinyl.
5. The process of claim 1, wherein the reaction is as follows:
or,
R1represents H, C1-C10 alkyl, R2，R3And in contrast, represents the residue of a compound to be alkylated by B (3)/B (3,6) -o-carborane, Ar represents a substituted or unsubstituted phenyl, monocyclic, bicyclic or tricyclic aromatic group or a monocyclic, bicyclic or tricyclic heterocyclic aromatic group containing one or more heteroatoms of N, O, S, and n is an integer of 1 to 5.
6. The method of claim 5, wherein R is2，R3Represents a substituted or unsubstituted alkyl group having H, C1-C8, C3-C8 cycloalkyl, C1-C8 alkoxy, C1-C8 haloalkyl, C1-C8 ester, aldehyde, halogen, cyano, amine, carbonyl, amide, sulfone, sulfoxide, sulfide, sulfonamide, nitro, phosphonyl, trifluoromethyl, trifluoromethoxy, thiotrifluoromethyl, alkenyl, fluoroalkyl, polyfluoroaryl, aryl, glycosyl, purinyl, pyrimidinePhenyl substituted by one or more of phenyl, biphenyl, naphthyl, pyridyl, thienyl, furyl, thiazolyl, oxazolyl and imidazolyl, wherein Ar represents phenyl substituted by one or more of H, C1-10 alkyl, C1-10 alkoxy, C1-10 ester and halogen, naphthyl, anthryl, furyl, thienyl, pyrrolyl, thiazolyl, imidazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, quinolyl, pteryl and acridinyl, and n is 2 or 3.
7. The method of claim 6, wherein R is2、R3Represents:
ar represents phenyl, thienyl, furyl, pyridyl and pyrimidyl which are substituted by one or more of H, methyl, ethyl, propyl, isopropyl, butyl and tert-butyl.
8. The process according to any one of claims 1 to 7, wherein the reaction temperature is 130-150 ℃ and the reaction solvent is one or more selected from the group consisting of toluene, o-xylene, m-xylene and p-xylene.
9. The method as set forth in claim 1, characterized in that carboxyl or acyl chloride or acyl bromide groups in the structure of the compound are utilized, or the compound is converted through derivatization reaction and then is connected with carboxyl or acyl chloride or acyl bromide groups, and the compound is reacted with diimide to obtain active amide with N-acyl-diimide groups.
10. The method of claim 1, further comprising subjecting the resulting B (3)/B (3,6) -o-carborane alkylate to a further conversion after the reaction is complete, said conversion comprising one or more of removal of an imine group on an o-carborane caged carbon, substitution of an unsubstituted carbon terminus of the carborane, boronization of the carborane, or derivatization of the compound.
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| CN114736228A (en) * | 2022-04-11 | 2022-07-12 | 陕西师范大学 | O-carborane modified pyromellitic acid diimide derivative-based fluorescent sensing film, and preparation method and application thereof |
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| CN114591357A (en) * | 2022-03-07 | 2022-06-07 | 郑州大学 | Synthesis method of B (9) -amido-o-carborane compound |
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| CN114736228A (en) * | 2022-04-11 | 2022-07-12 | 陕西师范大学 | O-carborane modified pyromellitic acid diimide derivative-based fluorescent sensing film, and preparation method and application thereof |
| CN114736228B (en) * | 2022-04-11 | 2024-01-30 | 陕西师范大学 | Fluorescence sensing film based on pyromellitic acid diimide derivative modified by o-carborane, preparation method and application |
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