CN113683474A - 一种降冰片烷类化合物的合成方法 - Google Patents
一种降冰片烷类化合物的合成方法 Download PDFInfo
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- CN113683474A CN113683474A CN202111016606.0A CN202111016606A CN113683474A CN 113683474 A CN113683474 A CN 113683474A CN 202111016606 A CN202111016606 A CN 202111016606A CN 113683474 A CN113683474 A CN 113683474A
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- norbornane
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- -1 norbornane compound Chemical class 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000002194 synthesizing effect Effects 0.000 title claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 56
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims abstract description 26
- BMWDUGHMODRTLU-UHFFFAOYSA-N azanium;trifluoromethanesulfonate Chemical compound [NH4+].[O-]S(=O)(=O)C(F)(F)F BMWDUGHMODRTLU-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000003446 ligand Substances 0.000 claims abstract description 10
- 150000002847 norbornane derivatives Chemical class 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 239000012043 crude product Substances 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000004440 column chromatography Methods 0.000 claims description 13
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 8
- 239000011736 potassium bicarbonate Substances 0.000 claims description 8
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 8
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 235000011181 potassium carbonates Nutrition 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 125000006189 4-phenyl benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- 125000000490 cinnamyl group Chemical group C(C=CC1=CC=CC=C1)* 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000006179 2-methyl benzyl group Chemical group [H]C1=C([H])C(=C(C([H])=C1[H])C([H])([H])*)C([H])([H])[H] 0.000 claims description 4
- 125000006180 3-methyl benzyl group Chemical group [H]C1=C([H])C(=C([H])C(=C1[H])C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000006283 4-chlorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1Cl)C([H])([H])* 0.000 claims description 4
- 125000004801 4-cyanophenyl group Chemical group [H]C1=C([H])C(C#N)=C([H])C([H])=C1* 0.000 claims description 4
- 125000004176 4-fluorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1F)C([H])([H])* 0.000 claims description 4
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims description 3
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 3
- BCJVBDBJSMFBRW-UHFFFAOYSA-N 4-diphenylphosphanylbutyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 BCJVBDBJSMFBRW-UHFFFAOYSA-N 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims 2
- 239000004327 boric acid Substances 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 abstract description 12
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 9
- 229910052736 halogen Inorganic materials 0.000 abstract description 6
- 150000002367 halogens Chemical class 0.000 abstract description 6
- 238000005859 coupling reaction Methods 0.000 abstract description 5
- 239000012445 acidic reagent Substances 0.000 abstract description 4
- 150000001543 aryl boronic acids Chemical class 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000001988 toxicity Effects 0.000 abstract description 3
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 28
- 239000002904 solvent Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical class OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- KPTRDYONBVUWPD-UHFFFAOYSA-N naphthalen-2-ylboronic acid Chemical compound C1=CC=CC2=CC(B(O)O)=CC=C21 KPTRDYONBVUWPD-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 3
- VOAAEKKFGLPLLU-UHFFFAOYSA-N (4-methoxyphenyl)boronic acid Chemical compound COC1=CC=C(B(O)O)C=C1 VOAAEKKFGLPLLU-UHFFFAOYSA-N 0.000 description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- 150000001499 aryl bromides Chemical class 0.000 description 2
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000012039 electrophile Substances 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- WZPWTXZSQHIABL-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl) benzoate Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1OC(=O)C1=CC=CC=C1 WZPWTXZSQHIABL-UHFFFAOYSA-N 0.000 description 1
- CAYQIZIAYYNFCS-UHFFFAOYSA-N (4-chlorophenyl)boronic acid Chemical compound OB(O)C1=CC=C(Cl)C=C1 CAYQIZIAYYNFCS-UHFFFAOYSA-N 0.000 description 1
- QWMJEUJXWVZSAG-UHFFFAOYSA-N (4-ethenylphenyl)boronic acid Chemical compound OB(O)C1=CC=C(C=C)C=C1 QWMJEUJXWVZSAG-UHFFFAOYSA-N 0.000 description 1
- COIQUVGFTILYGA-UHFFFAOYSA-N (4-hydroxyphenyl)boronic acid Chemical compound OB(O)C1=CC=C(O)C=C1 COIQUVGFTILYGA-UHFFFAOYSA-N 0.000 description 1
- 150000000183 1,3-benzoxazoles Chemical class 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000006181 4-methyl benzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])C([H])([H])* 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 150000001503 aryl iodides Chemical class 0.000 description 1
- 239000000022 bacteriostatic agent Substances 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 206010022000 influenza Diseases 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- OIRDBPQYVWXNSJ-UHFFFAOYSA-N methyl trifluoromethansulfonate Chemical compound COS(=O)(=O)C(F)(F)F OIRDBPQYVWXNSJ-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002848 norbornenes Chemical class 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229940002612 prodrug Drugs 0.000 description 1
- 239000000651 prodrug Substances 0.000 description 1
- 201000000980 schizophrenia Diseases 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- QNMBSXGYAQZCTN-UHFFFAOYSA-N thiophen-3-ylboronic acid Chemical compound OB(O)C=1C=CSC=1 QNMBSXGYAQZCTN-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- MNESLHFFAVMPAT-UHFFFAOYSA-N trifluoromethanesulfonate;trimethylazanium Chemical compound C[NH+](C)C.[O-]S(=O)(=O)C(F)(F)F MNESLHFFAVMPAT-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/32—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by introduction of halogenated alkyl groups into ring compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/08—Hydrogen atoms or radicals containing only hydrogen and carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/24—Phosphines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
Abstract
本发明提供了一种降冰片烷类化合物的合成方法，该方法在钯金属催化剂、配体和碱的催化作用下N,N,N‑三甲基三氟甲磺酸铵盐和芳硼酸类化合物以及降冰片烯的三组分偶联制备降冰片烷类化合物。该方法具有原料廉价易得、反应操作简单、条件温和、高效、经济等优点；所采用的N,N,N‑三甲基三氟甲磺酸铵盐可代替传统的有机卤作为新型的亲电试剂，可以解决使用有机卤所带来的毒性及对环境的危害。并且反应适用性广泛，可拓展至普通且高效的芳硼酸试剂。
Description
【技术领域】
本发明属于有机合成领域，具体涉及一种降冰片烷类化合物的合成方法。
【背景技术】
降冰片烷类化合物是功能材料分子、药物分子以及农药分子中重要的组成结构，并且具有良好的生物活性。例如其中一些含有降冰片烷分子片段的酯类化合物可作为抑菌剂、抗流感病毒药物前体等，部分含有降冰片烷分子片段的酰胺类化合物被证实是治疗精神分裂的有效药物。因此，降冰片烷类化合物在有机合成及工业生产方面具有良好的应用。
烯烃的双官能团化反应是制备降冰片烷的方法之一，同时也是一类重要的有机化学反应，它可以将比较容易获得的烯烃转化为具有高度官能团骨架的复杂分子。该策略可以在碳碳双键(C=C)上引入其他的官能团，进而增加分子的复杂性，为非常规键的形成打开了新的大门。其中带有过渡金属催化的烯烃双官能团化反应因其更加简洁的反应步骤和较高的原子经济性，受到了越来越广泛的关注。
1982年，Catellani等人报道了钯催化降冰片烯与芳基溴化物、炔烃进行的三组分双官能团化反应，这是降冰片烯双官能团化反应的首次报道，此反应以中等产率制备得到了相应产物（Tetrahedron1982, 23, 451）；2016年，宋秋玲课题组报道了钯催化芳基卤、降冰片烯与双硼试剂剂的三组分偶联反应，其中芳基溴及芳基碘均可以较优秀产率得到目标产物。但是上述两种合成降冰片烷及其衍生物的方法中均采用了有机卤试剂作为亲电试剂，但是有机卤试剂并非天然存在，价格昂贵且具有高毒性，容易对环境造成污染（J. Org. Chem.2016, 81, 1000−1005）；2019年，江焕峰课题组报道了钯催化烯丙基羧酸酯、降冰片烯及双硼试剂的三组分偶联反应，该反应可构建C(sp3)-C(sp3)和C(sp3)-B键，该反应可以中等至优秀的产率得到相应产物，但是底物适用性范围较窄，对于构建的C(sp3)-B键的硼试剂仅联硼酸频那醇酯可适用（Chin. J. Chem.2019, 37, 140−147）；2020年，SiyeonJeong报道了钯催化杂芳基卤化物、降冰片烯及苯并唑类化合物的多组分偶联反应。此反应可得到相应的顺式产物，但是产率大多在60%左右，并且反应中使用的杂芳基卤化物并不是一种廉价易得的亲电试剂（Org. Lett.2020, 22, 9670−9676）；2021年，Levi M. Stanley课题组报道了钯催化苯甲酸五氟苯酯与降冰片烯及四芳基硼酸盐的三组分偶联反应。此反应可以优秀产率的到相应产物，但是反应中烯烃用量需要增加至5-10当量，与原子经济性的概念并不符合，并且反应中采用的芳基硼试剂仅限于四苯基硼酸钠，并不能拓展至普遍的芳硼酸试剂（Org. Lett.2021, 23, 3507−3512）。
针对上述方法的不足，我们开发出一种更加高效的降冰片烷的合成方法，该方法具有原材料廉价易得、条件温和、原子经济性高等优点。其中，我们所采用的原料N,N,N-三甲基三氟甲磺酸铵盐，是一种可由廉价易得的有机胺类与三氟甲磺酸甲酯一步制备得到的季铵盐类化合物。它可代替传统的有机卤作为新型的亲电试剂，可以解决使用有机卤所带来的毒性及对环境的危害。并且反应适用性广泛，可拓展至普通且高效的芳硼酸试剂。
【发明内容】
本发明的目的在于提供一种以N,N,N-三甲基三氟甲磺酸铵盐和苯硼酸类化合物以及降冰片烯为原料，在钯金属催化剂、配体和碱的催化作用下制备降冰片烷类化合物的方法。
为达到上述发明目的，本发明提出以下技术方案：
一种降冰片烷类类化合物的合成方法,其中将冰片烷类化合物的结构如式I所示：
其中所述R1为1-萘、1-萘甲基、2-萘甲基、苄基、2-甲基苄基、3-甲基苄基、4-甲基苄基、4-苯基苄基、4-氟苄基、4-氯苄基、4-乙酰基苄基、4-甲酸甲酯苄基、二茂铁甲基、肉桂基中的一种；R2为苯基、4-甲基苯基、4-甲氧基苯基、2,4,6,-三甲基苯基、4-氟苯基、4-氯苯基、4-叔丁基苯基、4-联苯基、4-氰基苯基、4-乙烯基苯基、3-噻吩、3-呋喃中的一种。
其中化合物I的合成法，其特征在于，将原料N,N,N-三甲基三氟甲磺酸铵盐、苯硼酸类化合物、降冰片烯以及钯催化剂、配体、碱、有机溶剂置于反应容器中混合，在惰性气体环境下于80 ~ 120 oC搅拌反应2 ~ 8小时；反应结束后，减压蒸馏浓缩除去有机溶剂，粗产品经柱色谱分离，即得如式I所示的降冰片烷类化合物。
1.所述合成方法中，其原料N,N,N-三甲基三氟甲磺酸铵盐和苯硼酸类化合物以及降冰片烯的结构分别如式II、式III、式IV、式V和式VI及式VII所示：
其中所述式II中R1为1-萘、1-萘甲基、2-萘甲基、苄基、2-甲基苄基、3-甲基苄基、4-甲基苄基、4-苯基苄基、4-氟苄基、4-氯苄基、4-乙酰基苄基、4-甲酸甲酯苄基、二茂铁甲基、肉桂基中的一种；式III中R2为苯基、4-甲基苯基、4-甲氧基苯基、2,4,6,-三甲基苯基、4-氟苯基、4-氯苯基、4-叔丁基苯基、4-联苯基、4-氰基苯基、4-乙烯基苯基、3-噻吩、3-呋喃中的一种。
所述合成方法中，碱选自碳酸钾、碳酸氢钾、三乙胺中的至少一种。
所述合成方法中，钯金属催化剂选自(1,5-环辛二烯)二氯化钯、四三苯基膦钯中的至少一种。
所述合成方法中，配体选自1,4-双(二苯基膦)丁烷、三苯基膦中的至少一种。
所述合成方法中，N,N,N-三甲基三氟甲磺酸铵盐、芳硼酸类化合物、降冰片烯、碱、钯催化剂、配体的摩尔比为1：[1.0 ~ 1.4] : [1.5 ~ 3.0] : [1.0 ~ 1.5] ：[0.005~0.05] : [0 ~ 0.05]。
所述合成方法中，有机溶剂选自二氧六环、乙腈、四氢呋喃、乙二醇二甲醚、N,N-二甲基甲酰胺中的至少一种。
所述合成方法中，惰性气体选自氮气、氩气、氦气中的至少一种。
根据实验结果，本发明所提供的在钯金属催化剂、配体和碱的催化作用下N,N,N-三甲基三氟甲磺酸铵盐和芳硼酸类化合物以及降冰片烯的三组分偶联，合成降冰片烷类化合物的方法。该方法具有原料廉价易得、反应操作简单、条件温和、高效、经济等优点；所采用的N,N,N-三甲基三氟甲磺酸铵盐可代替传统的有机卤作为新型的亲电试剂，可以解决使用有机卤所带来的毒性及对环境的危害。并且反应适用性广泛，可拓展至普通且高效的芳硼酸试剂。
【附图说明】
附图1所示是本发明所提供的将冰片烷类化合物的合成路线图。
【具体实施方式】
下面结合本发明的合成例对本发明所述的合成方法作进一步说明：
如图1所示，本发明提供的一种降冰片烷类化合物的合成步骤为：取N,N,N-三甲基三氟甲磺酸铵盐、芳硼酸类化合物（摩尔比100 %-150%基于N,N,N-三甲基三氟甲磺酸铵盐）以及降冰片烯（摩尔比150 %-300%基于N,N,N-三甲基三氟甲磺酸铵盐）、钯催化剂（摩尔比0.5%-5%基于N,N,N-三甲基三氟甲磺酸铵盐）、碱（摩尔比100 %-150%基于N,N,N-三甲基三氟甲磺酸铵盐）、配体（摩尔比0 %-5%基于N,N,N-三甲基三氟甲磺酸铵盐）以及有机溶剂置于反应容器中混合，在氮气环境下于80 ~120 oC搅拌反应2 ~ 8小时；反应结束后，减压蒸馏浓缩除去有机溶剂，粗产品经柱色谱分离，即得目标产物。
下面结合具体的制备实例对本发明做进一步说明：
合成例1
其中，R1 = 1-萘甲基；R2 = 苯基。
在反应器中加入N,N,N-三甲基-1-甲基萘三氟甲磺酸铵盐0.2 mmol、苯硼酸0.28mmol、降冰片烯0.3 mmol、碳酸氢钾0.2 mmol、四三苯基膦钯5mol%、溶剂四氢呋喃2 mL。在氮气环境下加热到80 oC，持续搅拌6小时，停止反应并冷却至室温，减压蒸馏除去溶剂，粗产品经柱色谱分离即得目标产物，产率93%。
1H NMR (400 MHz, CDCl3) δ 7.78 (d, J = 8.0 Hz, 1H), 7.72 (d, J = 7.6Hz, 1H), 7.57 (d, J = 8.0 Hz, 1H), 7.41–7.33 (m, 2H), 7.28–7.22 (m, 5H),7.14–7.12 (m, 1H), 7.05 (d, J = 6.8 Hz, 1H), 2.97 (d, J = 9.2 Hz, 1H), 2.47(d, J = 16.0 Hz, 2H), 2.26 (t, J = 10.0 Hz, 1H), 2.04–1.98 (m, 3H), 1.53–1.39(m, 2H), 1.26 (d, J = 7.6 Hz, 2H), 1.00 (d, J = 7.6 Hz, 1H).
合成例2
其中，R1 = 1-萘甲基；R2 = 4-甲氧基苯基。
在反应器中加入N,N,N-三甲基-1-甲基萘三氟甲磺酸铵盐0.2 mmol、4-甲氧基苯硼酸0.28 mmol、降冰片烯0.3 mmol、碳酸氢钾0.2 mmol、四三苯基膦钯5mol%、溶剂四氢呋喃2 mL。在氮气环境下加热到80 oC，持续搅拌6小时，停止反应并冷却至室温，减压蒸馏除去溶剂，粗产品经柱色谱分离即得目标产物，产率94%。1H NMR (400 MHz, CDCl3) δ 7.86–7.79 (m, 2H), 7.65 (d, J = 8.4 Hz, 1H), 7.49–7.41 (m, 2H), 7.35–7.27 (m, 3H),7.14 (d, J = 7.2 Hz, 1H), 6.89 (d, J = 8.8 Hz, 2H), 3.80 (s, 3H), 3.00 (d, J= 8.8 Hz, 1H), 2.58–2.52 (m, 2H), 2.32–2.27 (m, 1H), 2.12–2.03 (m, 3H), 1.61–1.57 (m, 1H), 1.53–1.45 (m, 1H), 1.36–1.31 (m, 2H), 1.10–1.03 (m, 1H).
合成例3
其中，R1 = 1-萘甲基；R2 = 4-氯苯基。
在反应器中加入N,N,N-三甲基-1-甲基萘三氟甲磺酸铵盐0.2 mmol、4-氯苯硼酸0.28 mmol、降冰片烯0.3 mmol、碳酸氢钾0.2 mmol、四三苯基膦钯5mol%、溶剂四氢呋喃2mL。在氮气环境下加热到80 oC，持续搅拌6小时，停止反应并冷却至室温，减压蒸馏除去溶剂，粗产品经柱色谱分离即得目标产物，产率82%。
1H NMR (400 MHz, CDCl3) δ 7.81 (d, J = 8.4 Hz, 2H), 7.66 (d, J = 8.0Hz, 1H), 7.49–7.41 (m, 2H), 7.35–7.32 (m, 1H), 7.31–7.27 (m, 4H), 7.13 (d, J= 6.8 Hz, 1H), 3.01 (d, J = 8.8 Hz, 1H), 2.54–2.49 (m, 2H), 2.36–2.30 (m,1H), 2.10 (d, J = 13.6 Hz, 1H), 2.06–2.00 (m, 2H), 1.62–1,53 (m, 1H), 1.50–1.45 (m, 1H), 1.35–1.30 (m, 2H), 1.10–1.04 (m, 1H).
合成例4
其中，R1 = 1-萘甲基；R2 = 4-羟基苯基。
在反应器中加入N,N,N-三甲基-1-甲基萘三氟甲磺酸铵盐0.2 mmol、4-羟基苯硼酸0.28 mmol、降冰片烯0.3 mmol、碳酸氢钾0.2 mmol、四三苯基膦钯5mol%、溶剂四氢呋喃2mL。在氮气环境下加热到80 oC，持续搅拌6小时，停止反应并冷却至室温，减压蒸馏除去溶剂，粗产品经柱色谱分离即得目标产物，产率90%。1H NMR (400 MHz, CDCl3) δ 7.85–7.80(m, 2H), 7.66 (d, J = 8.4 Hz, 1H), 7.49–7.41 (m, 2H), 7.35–7.31(m, 1H), 7.24–7.21 (m, 2H), 7.14 (d, J = 6.8 Hz, 1H), 6.84–6.80 (m, 2H), 4.66 (s, 1H), 2.99(d, J = 9.2 Hz, 1H), 2.58–2.50 (m, 2H), 2.32–2.26 (m, 1H), 2.09–2.02(m, 3H),1.56–1.45 (m, 2H), 1.31 (d, J = 10.0 Hz, 2H), 1.10–1.03 (m, 1H).
合成例5
其中，R1 = 1-萘甲基；R2 = 4-乙烯基苯基。
在反应器中加入N,N,N-三甲基-1-甲基萘三氟甲磺酸铵盐0.2 mmol、4-乙烯基苯硼酸0.28 mmol、降冰片烯0.3 mmol、碳酸氢钾0.2 mmol、四三苯基膦钯5mol%、溶剂四氢呋喃2 mL。在氮气环境下加热到80 oC，持续搅拌6小时，停止反应并冷却至室温，减压蒸馏除去溶剂，粗产品经柱色谱分离即得目标产物，产率75%。1H NMR (400 MHz, CDCl3) δ 7.86–7.78 (m, 2H), 7.65 (d, J = 8.0 Hz, 1H), 7.49–7.42 (m, 2H), 7.40–7.38 (m, 2H),7.33–7.30 (m, 3H), 7.13 (d, J = 6.8 Hz, 1H), 6.71 (dd, J 1 = 17.6, J 2 = 10.8Hz,1H), 5.72 (d, J = 18.4 Hz, 1H), 5.19 (d, J = 11.6 Hz, 1H), 3.03 (d, J = 9.2Hz, 1H), 2.58–2.54 (m, 2H), 2.36–2.30 (m, 1H), 2.13–2.04 (m, 3H), 1.61–1.54(m, 1H), 1.53–1.45 (m, 1H), 1.35–1.30 (m, 2H), 1.10–1.03 (m, 1H).
合成例6
其中，R1 = 1-萘甲基；R2 = 3-噻吩。
在反应器中加入N,N,N-三甲基-1-甲基萘三氟甲磺酸铵盐0.2 mmol、3-噻吩硼酸0.28 mmol、降冰片烯0.3 mmol、碳酸氢钾0.2 mmol、四三苯基膦钯5mol%、溶剂四氢呋喃2mL。在氮气环境下加热到80 oC，持续搅拌6小时，停止反应并冷却至室温，减压蒸馏除去溶剂，粗产品经柱色谱分离即得目标产物，产率85%。1H NMR (400 MHz, CDCl3) δ 7.87 (d, J= 8.0 Hz, 1H), 7.82–7.79 (m, 1H), 7.66 (d, J = 8.0 Hz, 1H), 7.50–7.41 (m,2H), 7.35–7.32 (m, 1H), 7.29–7.27 (m, 1H), 7.15 (d, J = 6.8 Hz, 1H), 7.12–7.08 (m, 2H), 3.13 (d, J = 8.8 Hz, 1H), 2.68–2.64 (m, 1H), 2.51 (d, J = 3.2Hz, 1H), 2.30–2.15 (m, 2H), 2.08–2.03 (m, 2H), 1.60–1.52 (m, 1H), 1.50–1.43(m, 1H), 1.34–1.27 (m, 2H), 1.08–1.01 (m, 1H).
合成例7
其中，R1 = 1-萘；R2 = 2-萘。
在反应器中加入N,N,N-三甲基-1-萘三氟甲磺酸铵盐0.2 mmol、2-萘硼酸0.28mmol、降冰片烯0.55 mmol、碳酸钾0.3 mmol、(1,5-环辛二烯)二氯化钯5mol%、1,4-双(二苯基膦)丁烷5mol%、溶剂乙二醇二甲醚1mL。在氮气环境下加热到110 oC，持续搅拌8小时，停止反应并冷却至室温，减压蒸馏除去溶剂，粗产品经柱色谱分离即得目标产物，产率53%。1HNMR (400 MHz, CDCl3) δ 8.09 (d, J = 8.8 Hz, 1H), 7.47 (d, J = 8.4 Hz, 1H),7.44–7.31 (m, 6H), 7.21–7.14 (m, 4H), 7.08 (d, J = 8.8 Hz, 1H), 6.85–6.83 (m,1H), 4.05 (d, J = 9.6 Hz, 1H), 3.62 (d, J = 9.6 Hz, 1H), 2.85 (s, 1H), 2.59–2.57 (m, 2H), 1.87–1.83 (m, 2H), 1.67–1.64 (m, 3H).
合成例8
其中，R1 = 苄基；R2 = 2-萘。
在反应器中加入N,N,N-三甲基-苄基三氟甲磺酸铵盐0.2 mmol、2-萘硼酸0.28mmol、降冰片烯0.55 mmol、碳酸钾0.3 mmol、四三苯基膦钯5mol%、溶剂乙腈：二氧六环1：1混合溶剂1mL。在氮气环境下加热到120 oC，持续搅拌2小时，停止反应并冷却至室温，减压蒸馏除去溶剂，粗产品经柱色谱分离即得目标产物，产率85%。1H NMR (400 MHz, CDCl3) δ7.81–7.77 (m, 2H), 7.73 (d, J = 8.4 Hz, 1H), 7.68 (s, 1H), 7.47–7.39 (m, 2H),7.38–7.34 (m, 1H), 7.18–7.15 (m, 2H), 7.10–7.07 (m, 1H), 6.98 (d, J = 7.2 Hz,2H), 3.13 (d, J = 9.2 Hz, 1H), 2.65 (s, 1H), 2.32–2.26 (m, 1H), 2.09–2.03 (m,3H), 1.78–1,71 (m, 1H), 1.66–1.55 (m, 2H), 1.42–1.34 (m, 2H), 1.25–1.23 (m,1H).
合成例9
其中，R1 = 4-甲基苄基；R2 = 2-萘。
在反应器中加入N,N,N-三甲基-（4-甲基苄基）三氟甲磺酸铵盐0.2 mmol、2-萘硼酸0.28 mmol、降冰片烯0.55 mmol、碳酸钾0.3 mmol、四三苯基膦钯5mol%、溶剂乙腈：二氧六环1：1混合溶剂1mL。在氮气环境下加热到120 oC，持续搅拌2小时，停止反应并冷却至室温，减压蒸馏除去溶剂，粗产品经柱色谱分离即得目标产物，产率90%。1H NMR (400 MHz,CDCl3) δ 7.84 (d, J = 8.4 Hz, 2H), 7.79 (d, J = 8.0 Hz, 2H), 7.73 (d, J = 8.4Hz, 1H), 7.67 (s, 1H), 7.47–7.39 (m, 2H), 7.35–7.33 (m, 1H), 7.03 (d, J = 8.0Hz, 2H), 3.86 (s, 3H), 3.14 (d, J = 9.2 Hz, 1H), 2.66 (s, 1H), 2.33–2.27 (m,1H), 2.13–2.08 (m, 1H), 2.05–2.01 (m, 2H), 1.86–1.79 (m, 1H), 1.65–1.58 (m,2H), 1.43–1.36 (m, 2H), 1.24–1.19 (m, 1H), 13C NMR (100 MHz, CDCl3) δ 140.9,139.4, 134.7, 133.4, 131.8, 128.7, 128.2, 127.6, 127.5, 127.1, 125.9, 125.8,125.0, 51.8, 50.3, 42.5, 39.1, 37.8, 34.8, 31.1, 29.3, 20.9.
合成例10
其中，R1 = 4-苯基苄基；R2 = 2-萘。
在反应器中加入N,N,N-三甲基-（4-苯基苄基）三氟甲磺酸铵盐0.2 mmol、2-萘硼酸0.28 mmol、降冰片烯0.55 mmol、碳酸钾0.3 mmol、四三苯基膦钯5mol%、溶剂乙腈：二氧六环1：1混合溶剂1mL。在氮气环境下加热到120 oC，持续搅拌2小时，停止反应并冷却至室温，减压蒸馏除去溶剂，粗产品经柱色谱分离即得目标产物，产率93%。1H NMR (400 MHz,CDCl3) δ 7.80 (d, J = 8.4 Hz, 2H), 7.75 (d, J = 8.4 Hz, 1H), 7.69 (s, 1H),7.55–7.53 (m, 2H), 7.46–7.36 (m, 7H), 7.31–7.27 (m, 1H), 7.04 (d, J = 8.0 Hz,2H), 3.16 (d, J = 9.2 Hz, 1H), 2.67 (s, 1H), 2.38–2.31 (m, 1H), 2.13–2.06 (m,3H), 1.85–1.79 (m, 1H), 1.67–1.61 (m, 2H), 1.45–1.37 (m, 2H), 1.29–1.25 (m,1H), 13C NMR (100 MHz, CDCl3) δ 141.7, 141.1, 140.9, 138.2, 133.4, 131.8,129.2, 128.6, 128.2, 127.6, 127.5, 127.2, 126.9, 126.7, 126.0, 125.8, 125.1,51.8, 50.1, 42.5, 39.4, 37.9, 34.9, 31.1, 29.3.
合成例11
其中，R1 = 肉桂基；R2 = 4-甲氧基苯基。
在反应器中加入N,N,N-三甲基-肉桂基三氟甲磺酸铵盐0.2 mmol、4-甲氧基苯硼酸0.28 mmol、降冰片烯0.55 mmol、碳酸钾0.3 mmol、四三苯基膦钯5mol%、溶剂乙腈：二氧六环1：1混合溶剂1mL。在氮气环境下加热到120 oC，持续搅拌2小时，停止反应并冷却至室温，减压蒸馏除去溶剂，粗产品经柱色谱分离即得目标产物，产率51%。1H NMR (400 MHz,CDCl3) δ 7.25 (d, J = 4.4 Hz, 4H), 7.16–7.14 (m, 1H), 7.10 (d, J = 8.4 Hz,2H), 6.81 (d, J = 8.8 Hz, 2H), 6.13 (d, J = 16.0 Hz, 1H), 6.06–5.99 (m, 1H),3.78 (s, 3H), 2.87 (d, J = 9.2 Hz, 1H), 2.43 (s, 1H), 2.21 (d, J = 2.8 Hz,1H), 2.01– 1.95 (m, 1H), 1.82 (d, J = 10.0 Hz, 1H), 1.67–1.57 (m, 3H), 1.49–1.41 (m, 1H), 1.37–1.25 (m, 3H). 13C NMR (100 MHz, CDCl3) δ 157.5, 138.0,135.4, 131.1, 130.1, 129.4, 128.4, 126.6, 125.8, 113.2, 55.2, 50.8, 48.6,42.5, 39.7, 35.7, 34.8, 31.1, 29.3.
需要说明的是，以上实施例并不构成对本发明要求保护范围的限制，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。
Claims (8)
1.一种降冰片烷类化合物的合成方法，包含下述步骤：
取原料N,N,N-三甲基三氟甲磺酸铵盐、芳硼酸类化合物和降冰片烯以及钯金属催化剂、配体、碱、有机溶剂置于反应容器中混合，在惰性气体环境下于80 ~ 120 oC搅拌反应2~ 8小时；反应结束后，减压蒸馏浓缩除去有机溶剂，粗产品经柱色谱分离，即得如式I所示的降冰片烷类化合物：
所述式I中，
R1为1-萘、1-萘甲基、2-萘甲基、苄基、2-甲基苄基、3-甲基苄基、4-甲基苄基、4-苯基苄基、4-氟苄基、4-氯苄基、4-乙酰基苄基、4-甲酸甲酯苄基、二茂铁甲基、肉桂基；
R2为苯基、4-甲基苯基、4-甲氧基苯基、2,4,6,-三甲基苯基、4-氟苯基、4-氯苯基、4-叔丁基苯基、4-联苯基、4-氰基苯基、4-乙烯基苯基、3-噻吩、3-呋喃。
2.根据权利要求1所述的降冰片烷类化合物的合成方法，其特征在于，所述合成方法中使用的原料N,N,N-三甲基三氟甲磺酸铵盐、芳硼酸类化合物以及降冰片烯的结构分别如式II、式III及式IV所示：
所述式II中，
R1为1-萘、1-萘甲基、2-萘甲基、苄基、2-甲基苄基、3-甲基苄基、4-甲基苄基、4-苯基苄基、4-氟苄基、4-氯苄基、4-乙酰基苄基、4-甲酸甲酯苄基、二茂铁甲基、肉桂基；
所述式III中，
R2为苯基、4-甲基苯基、4-甲氧基苯基、2,4,6,-三甲基苯基、4-氟苯基、4-氯苯基、4-叔丁基苯基、4-联苯基、4-氰基苯基、4-乙烯基苯基、3-噻吩、3-呋喃。
3.根据权利要求1所述的降冰片烷类化合物的合成方法，其特征在于，所述碱选自碳酸钾、碳酸氢钾、三乙胺中的至少一种。
4.根据权利要求1所述的降冰片烷类化合物的合成方法，其特征在于，所述钯金属催化剂选自(1,5-环辛二烯)二氯化钯、四三苯基膦钯中的至少一种。
5.根据权利要求1所述的降冰片烷类化合物的合成方法，其特征在于，所述配体选自1,4-双(二苯基膦)丁烷、三苯基膦中的至少一种。
6.根据权利要求1所述的降冰片烷类化合物的合成方法，其特征在于，所述N,N,N-三甲基三氟甲磺酸铵盐、芳硼酸类化合物、降冰片烯、碱、钯催化剂、配体的摩尔比为1：[1.0 ~1.4] : [1.5 ~ 2.75] : [1.0 ~ 1.5] ：[0.005~ 0.05] : [0 ~ 0.05]。
7.根据权利要求1所述的降冰片烷类化合物的合成方法，其特征在于，所述有机溶剂选自二氧六环、乙腈、四氢呋喃、乙二醇二甲醚、N,N-二甲基甲酰胺中的至少一种。
8.根据权利要求1所述的降冰片烷类化合物的合成方法，其特征在于，所述惰性气体选自氮气、氩气、氦气中的至少一种。
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