CN113201006B - 一种铑催化的碳氢活化反应合成酰基硅取代的异吲哚-1-酮类似物的方法 - Google Patents
一种铑催化的碳氢活化反应合成酰基硅取代的异吲哚-1-酮类似物的方法 Download PDFInfo
- Publication number
- CN113201006B CN113201006B CN202110551139.5A CN202110551139A CN113201006B CN 113201006 B CN113201006 B CN 113201006B CN 202110551139 A CN202110551139 A CN 202110551139A CN 113201006 B CN113201006 B CN 113201006B
- Authority
- CN
- China
- Prior art keywords
- rhodium
- substituted
- silicon
- acyl
- additive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 17
- 239000010703 silicon Substances 0.000 title claims abstract description 17
- 230000004913 activation Effects 0.000 title claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 7
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 5
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 5
- -1 N-substituted benzamide Chemical class 0.000 claims abstract description 23
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 229910052723 transition metal Inorganic materials 0.000 claims abstract 4
- 150000003624 transition metals Chemical class 0.000 claims abstract 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 12
- 239000010948 rhodium Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 229910052703 rhodium Inorganic materials 0.000 claims description 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 150000003936 benzamides Chemical class 0.000 claims description 7
- 239000003921 oil Substances 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- 238000010898 silica gel chromatography Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 6
- QVLTVILSYOWFRM-UHFFFAOYSA-L CC1=C(C)C(C)([Rh](Cl)Cl)C(C)=C1C Chemical compound CC1=C(C)C(C)([Rh](Cl)Cl)C(C)=C1C QVLTVILSYOWFRM-UHFFFAOYSA-L 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 6
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 6
- KXDAEFPNCMNJSK-UHFFFAOYSA-N benzene carboxamide Natural products NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 238000005859 coupling reaction Methods 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 claims description 3
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 3
- 229940071536 silver acetate Drugs 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- SAXQOYZKDFVDTH-UHFFFAOYSA-N CC1=C(C(=C(C1(C)[Rh])C)C)C Chemical compound CC1=C(C(=C(C1(C)[Rh])C)C)C SAXQOYZKDFVDTH-UHFFFAOYSA-N 0.000 claims description 2
- 229940054066 benzamide antipsychotics Drugs 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- MBAKFIZHTUAVJN-UHFFFAOYSA-I hexafluoroantimony(1-);hydron Chemical compound F.F[Sb](F)(F)(F)F MBAKFIZHTUAVJN-UHFFFAOYSA-I 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 230000009471 action Effects 0.000 claims 1
- 125000002252 acyl group Chemical group 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- XTBAPWCYTNCZTO-UHFFFAOYSA-N isoindol-1-one Chemical class C1=CC=C2C(=O)N=CC2=C1 XTBAPWCYTNCZTO-UHFFFAOYSA-N 0.000 claims 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims 1
- 150000003376 silicon Chemical class 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 3
- 229910000077 silane Inorganic materials 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 238000010499 C–H functionalization reaction Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- RGUXIKNUAIQXNW-UHFFFAOYSA-N 1-[tert-butyl(dimethyl)silyl]prop-2-en-1-one Chemical compound CC(C)(C)[Si](C)(C)C(=O)C=C RGUXIKNUAIQXNW-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 150000001345 alkine derivatives Chemical class 0.000 description 3
- 150000008430 aromatic amides Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000006254 arylation reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000005691 oxidative coupling reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- UCXDWSTYBSBFFB-UHFFFAOYSA-L 1-methyl-4-propan-2-ylbenzene;ruthenium(2+);dichloride Chemical class Cl[Ru]Cl.CC(C)C1=CC=C(C)C=C1 UCXDWSTYBSBFFB-UHFFFAOYSA-L 0.000 description 1
- HDYFAPRLDWYIBU-UHFFFAOYSA-N 1-silylprop-2-en-1-one Chemical class [SiH3]C(=O)C=C HDYFAPRLDWYIBU-UHFFFAOYSA-N 0.000 description 1
- LZPWAYBEOJRFAX-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2$l^{2}-dioxaborolane Chemical compound CC1(C)O[B]OC1(C)C LZPWAYBEOJRFAX-UHFFFAOYSA-N 0.000 description 1
- WDBQJSCPCGTAFG-QHCPKHFHSA-N 4,4-difluoro-N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclohexane-1-carboxamide Chemical compound FC1(CCC(CC1)C(=O)N[C@@H](CCN1CCC(CC1)N1C(=NN=C1C)C(C)C)C=1C=NC=CC=1)F WDBQJSCPCGTAFG-QHCPKHFHSA-N 0.000 description 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
- WREVVZMUNPAPOV-UHFFFAOYSA-N 8-aminoquinoline Chemical group C1=CN=C2C(N)=CC=CC2=C1 WREVVZMUNPAPOV-UHFFFAOYSA-N 0.000 description 1
- 241001120493 Arene Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010485 C−C bond formation reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000006957 Michael reaction Methods 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- 238000007296 Stetter synthesis reaction Methods 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 229940051881 anilide analgesics and antipyretics Drugs 0.000 description 1
- 150000003931 anilides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000006795 borylation reaction Methods 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000026045 iodination Effects 0.000 description 1
- 238000006192 iodination reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000006487 oxidative cycloaddition reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/083—Syntheses without formation of a Si-C bond
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
本发明公开了一种铑催化的碳氢活化反应合成酰基硅取代的异吲哚‑1‑酮类化合物的方法。本发明以N‑取代苯甲酰胺和α,β‑不饱和酰基硅为原料，在添加剂的辅助下，通过过渡金属催化的碳氢活化反应高效地构建酰基硅取代的异吲哚‑1‑酮结构。该方法避免了传统的线性合成方法经济性低，反应条件苛刻的问题，是一种简单、温和的替代传统合成酰基硅烷的方法，并且具有广泛的底物适用性，具有广阔的应用前景。
Description
技术领域
本发明涉及一种铑催化的N-取代苯甲酰胺与α,β-不饱和酰基硅的C-H活化反应构建酰基硅取代的异吲哚-1-酮类似物的新方法，属于有机化学技术领域。
背景技术
C-H键活化一直是有机化学合成的研究热点之一。C-H键活化是在导向基团的辅助下，反应位点处的C-H和金属中心配位，形成较稳定的五元或六元环状金属中间体，从而使分子内C-H键选择性活化的过程。由于它具有原子经济性高、底物范围广、反应条件温和等特点,已经渐渐成为构建C-C键、C-杂键等最有吸引力的策略。1其中，铑催化剂因其高的官能团耐受性和广泛的合成用途而在通过C-H活化途径进行的C-C偶联反应领域中脱颖而出。2近年来，酰胺作为重要的C-H活化导向基团也已经被广泛关注3，如酰胺为导向基与α,β-不饱和羧酸酯和炔等都有C-H活化研究的报道。4
其次，酰基硅是一个重要的合成分子，在有机化学、材料化学以及光化学中有着广泛的使用。由于酰基硅烷的电子特性导致其反应性与其他羰基化合物不同，可以产生独一无二的反应特性，比如可以产生α-硅氧负离子、酰基负离子、α-硅氧卡宾。因此，在过去的几十年里，酰基硅烷的合成应用受到了很大的关注。虽然已有报道酰基硅烷的合成方法，但传统的线性合成方法既不经济，又面临反应条件苛刻的问题，这可能限制酰基硅烷的合成范围，特别是那些高度功能化的合成方法。因此，开发一种新的合成方法，简化功能化酰基硅烷的合成途径，仍然是非常可取的一种方法，具有重要的意义5。
发明内容
针对传统的线性合成酰基硅烷方法，采用C-H活化反应构建异吲哚-1-酮类似物的新方法，本发明的目的是提供一种铑催化的N-取代苯甲酰胺与α,β-不饱和酰基硅的C-H活化反应构建酰基硅取代的异吲哚-1-酮类似物，该发明方法是一种简单、温和的替代传统合成酰基硅烷的方法，具有广阔的应用前景。
为实现上述目的，本发明采用以下技术方案：
以N-取代苯甲酰胺与α，β不饱和酰基硅为起始原料，其化学反应式如下：
其中：
R1为氢、甲基、甲氧基、硝基、卤素中的一种；
R2为苯基，甲基、甲氧基、硝基、卤素取代的苯基中的一种；
其制备步骤如下：
在氩气保护下，在洁净的耐压瓶中依次加入N-取代苯甲酰胺、α,β-不饱和酰基硅、催化剂、添加剂和溶剂，放入100℃油浴中反应36h；
反应结束后，减压除去溶剂，用硅胶柱层析纯化得到产品。
其特征在于催化剂为二氯（五甲基环戊二烯基）合铑（Ⅲ）、(二(六氟锑酸)三乙腈(五甲基环戊二烯基)铑(III))、对伞花烃二氯化钌二聚体中的一种；
溶剂为乙腈、四氢呋喃、1，2-二氯乙烷、甲苯、丙酮的一种；
添加剂为碳酸银、乙酸银、醋酸铜、一水合醋酸铜的一种。步骤中N-取代苯甲酰胺：α，β不饱和酰基硅：催化剂：添加剂的摩尔比为1：（2.0-4.0）：（0.05-0.1）：（1.5-2.5）。
本发明采取以上技术方案，其具有以下优点：相比于传统的合成酰基硅取代的异吲哚-1-酮类似物，该发明方法是一种简单、温和的替代传统的合成方法，并且具有广泛的底物适用性，具有广阔的前景。
核磁共振氢谱（1H NMR）、碳谱（13C NMR）以及高分辨质谱证实了合成的化合物的结构。其中核磁共振图采用Varian INOVA-400型核磁共振仪测定，以四甲基硅烷（TMS）为内标（δ0 ppm），氘代氯仿为溶剂；高分辨质谱用Agilent 1946B质谱仪测定。
具体实施方式
下面结合具体实施方式对本发明作进一步描述，有助于对本发明的理解。但并不能以此来限制本发明的权利范围，而本发明的权利范围应以权利要求书阐述的为准。
实施案例1：化合物1的合成
氩气条件下，在洁净的耐压瓶中依次加入N-取代苯甲酰胺（21.1mg，0.1mmol）、1-（叔丁基二甲基甲硅烷基）丙-2-烯-1-酮（51mg，0.3mmol）、二氯（五甲基环戊二烯基）合铑（Ⅲ）（3.1mg，0.005mmol）、碳酸银（55.2mg、0.2mmol）、乙腈（1.5ml），置于100℃油浴中搅拌36h。
反应结束后，减压除去溶剂，用硅胶柱层析纯化得到产品即淡黄色固体，熔点范围为150.5-151.7℃，收率为83%。1H NMR (400 MHz, Chloroform-d) δ 7.79 (d, J = 7.8Hz, 1H), 7.55 (d, J = 7.4 Hz, 2H), 7.44 – 7.38 (m, 2H), 7.29 (d, J = 7.8 Hz,1H), 7.20 (t, J = 7.4 Hz, 1H), 7.17 (s, 1H), 5.82 (dd, J = 8.4, 3.2 Hz, 1H),3.13 (dd, J = 18.6, 3.2 Hz, 1H), 2.82 (dd, J = 18.6, 8.5 Hz, 1H), 2.44 (s,3H), 0.85 (s, 9H), 0.08 (d, J = 10.9 Hz, 6H)；13C NMR (101 MHz, Chloroform-d) δ245.53, 167.03, 146.04, 143.01, 136.77, 129.51, 129.28, 129.20, 125.33,123.92, 123.25, 123.11, 54.92, 53.28, 26.27, 21.99, 16.58, -7.24, -7.36. HRMS(ESI): m/z计算值C23H30NO2Si+: 380.5825，实测值: 380.5823。
实施案例2：化合物2的合成
氩气条件下，在洁净的耐压瓶中依次加入N-取代苯甲酰胺（27.5mg，0.1mmol）、1-（叔丁基二甲基甲硅烷基）丙-2-烯-1-酮（51mg，0.3mmol）、二(六氟锑酸)三乙腈(五甲基环戊二烯基)铑(III))（8.3mg，0.01mmol）、碳酸银（55.2mg、0.2mmol）、乙腈（1.5ml），置于100℃油浴中搅拌36h。
反应结束后，减压除去溶剂，用硅胶柱层析纯化得到产品即淡黄色固体，熔点范围为169.5-171.3℃，收率为75%。1H NMR (400 MHz, Chloroform-d) δ 7.77 (d, J = 8.1Hz, 1H), 7.63 (dd, J = 8.1, 1.7 Hz, 1H), 7.56 (s, 1H), 7.52 (dd, J = 8.7, 1.2Hz, 2H), 7.45 – 7.40 (m, 2H), 7.26 – 7.20 (m, 1H), 5.81 (dd, J = 8.6, 3.1 Hz,1H), 3.16 (dd, J = 18.7, 3.2 Hz, 1H), 2.81 (dd, J = 18.7, 8.6 Hz, 1H), 0.85(s, 9H), 0.09 (d, J = 11.6 Hz, 6H).13C NMR (101 MHz, Chloroform-d) δ 245.13,165.96, 147.32, 136.28, 131.99, 130.80, 129.31, 126.95, 126.39, 125.78,125.54, 123.20, 54.88, 52.84, 26.26, 16.57, -7.25, -7.35。HRMS (ESI): m/z计算值C22H27BrNO2Si+: 444.0989，实测值: 444.0990。
实施案例3：化合物3的合成
氩气条件下，在洁净的耐压瓶中依次加入N-取代苯甲酰胺（22.7mg，0.1mmol）、1-（叔丁基二甲基甲硅烷基）丙-2-烯-1-酮（51mg，0.3mmol）、二氯（五甲基环戊二烯基）合铑（Ⅲ）（6.2mg，0.01mmol）、乙酸银（33.4mg、0.2mmol）、四氢呋喃（1.5ml），置于100℃油浴中搅拌36h。
反应结束后，减压除去溶剂，用硅胶柱层析纯化得到产品即淡黄色固体，熔点范围为94.9-96.3℃，收率为55%。1H NMR (400 MHz, Chloroform-d) δ 7.89 (d, J = 7.0 Hz,1H), 7.54 (td, J = 7.4, 1.4 Hz, 1H), 7.50 – 7.44 (m, 1H), 7.43 – 7.39 (m,2H), 7.37 (d, J = 6.4 Hz, 1H), 6.98 – 6.91 (m, 2H), 5.76 (dd, J = 8.2, 3.6Hz, 1H), 3.82 (s, 3H), 3.12 (dd, J = 18.6, 3.6 Hz, 1H), 2.80 (dd, J = 18.6,8.2 Hz, 1H), 0.84 (s, 9H), 0.08 (d, J = 14.6 Hz, 6H).13C NMR (101 MHz,Chloroform-d) δ 245.11, 166.91, 157.52, 145.65, 132.01, 131.94, 129.39,128.43, 125.39, 123.99, 122.77, 114.50, 55.64, 55.51, 53.16, 26.28, 16.54, -7.21, -7.34. HRMS (ESI): m/z计算值C23H30NO3Si+: 396.1989，实测值: 396.1986。
实施案例4：化合物4的合成
氩气条件下，在洁净的耐压瓶中依次加入N-取代苯甲酰胺（23.1mg，0.1mmol）、1-（叔丁基二甲基甲硅烷基）丙-2-烯-1-酮（51mg，0.3mmol）、二氯（五甲基环戊二烯基）合铑（Ⅲ）（3.1mg，0.005mmol）、碳酸银（55.2mg、0.2mmol）、乙腈（1.5ml），置于100℃油浴中搅拌36h。
反应结束后，减压除去溶剂，用硅胶柱层析纯化得到产品即淡黄色固体，熔点范围为161.2-162.3℃，收率为78%。1H NMR (400 MHz, Chloroform-d) δ 7.90 (d, J = 7.5Hz, 1H), 7.59 – 7.46 (m, 4H), 7.37 (t, J = 7.9 Hz, 3H), 5.83 (dd, J = 8.4,3.2 Hz, 1H), 3.19 – 3.04 (m, 1H), 2.85 (dd, J = 19.0, 8.7 Hz, 1H), 0.86 (s,9H), 0.10 (d, J = 9.7 Hz, 6H)。13C NMR (101 MHz, Chloroform-d) δ 245.02,166.92, 145.52, 135.25, 132.48, 131.51, 130.76, 129.29, 128.62, 124.18,122.78, 54.94, 53.12, 26.28, 16.56, -7.21, -7.30. HRMS (ESI): m/z计算值C22H27ClNO2Si+: 400.1494，实测值:400.1492。
实施案例5：化合物5的合成
氩气条件下，在洁净的耐压瓶中依次加入N-取代苯甲酰胺（21.1mg，0.1mmol）、1-（叔丁基二甲基甲硅烷基）丙-2-烯-1-酮（51mg，0.3mmol）、二氯（五甲基环戊二烯基）合铑（Ⅲ）（6.2mg，0.01mmol）、碳酸银（55.2mg、0.2mmol）、乙腈（1.5ml），置于100℃油浴中搅拌36h。
反应结束后，减压除去溶剂，用硅胶柱层析纯化得到产品即淡黄色固体，熔点范围为129.7-132.3℃，收率为92%。1H NMR (400 MHz, Chloroform-d) δ 7.91 (d, J = 7.4Hz, 1H), 7.59 – 7.46 (m, 2H), 7.38 (d, J = 7.5 Hz, 2H), 7.33 – 7.28 (m, 2H),7.07 – 7.00 (m, 1H), 5.83 (dd, J = 8.5, 3.2 Hz, 1H), 3.17 (dd, J = 18.7, 3.2Hz, 1H), 2.81 (dd, J = 18.7, 8.4 Hz, 1H), 2.38 (s, 3H), 0.85 (s, 9H), 0.08(d, J = 11.1 Hz, 6H).13C NMR (101 MHz, Chloroform-d) δ 245.18, 166.93, 145.71,139.10, 136.51, 132.17, 131.92, 129.03, 128.45, 126.42, 124.06, 122.82,120.34, 55.22, 53.23, 26.28, 21.57, 16.54, -7.25, -7.33. HRMS (ESI): m/z计算值C23H30NO2Si+: 380.2040，实测值:380.2043。
参考文献
1.Schröder, N.; Wencel-Delord, J.; Glorius, F., High-Yielding,Versatile, and Practical [Rh(III)Cp*]-Catalyzed Ortho Bromination andIodination of Arenes. Journal of the American Chemical Society 2012,134,8298-8301.
2.Colby, D. A.; Bergman, R. G.; Ellman, J. A., Rhodium-Catalyzed C−CBond Formation via Heteroatom-Directed C−H Bond Activation. Chemical Reviews 2010,110, 624-655.
3.a) Boele, M. D.; van Strijdonck, G. P.; de Vries, A. H.; Kamer, P.C.; de Vries, J. G.; van Leeuwen, P. W., Selective Pd-catalyzed oxidativecoupling of anilides with olefins through C-H bond activation at roomtemperature. J Am Chem Soc 2002,124, 1586-7. b) Wang, J.-R.; Yang, C.-T.;Liu, L.; Guo, Q.-X., Pd-catalyzed aerobic oxidative coupling of anilides witholefins through regioselective C–H bond activation. Tetrahedron Letters 2007,48, 5449-5453. c)Wan, X.; Ma, Z.; Li, B.; Zhang, K.; Cao, S.; Zhang, S.; Shi,Z., Highly Selective C−H Functionalization/Halogenation of Acetanilide.Journal of the American Chemical Society 2006,128, 7416-7417.
4.a) Wang, F.; Song, G.; Li, X., Rh(III)-Catalyzed Tandem OxidativeOlefination−Michael Reactions between Aryl Carboxamides and Alkenes. OrganicLetters 2010, 12, 5430-5433. b)Song, G.; Chen, D.; Pan, C.-L.; Crabtree, R.H.; Li, X., Rh-Catalyzed Oxidative Coupling between Primary and SecondaryBenzamides and Alkynes: Synthesis of Polycyclic Amides. The Journal ofOrganic Chemistry 2010, 75, 7487-7490. c)Shiota, H.; Ano, Y.; Aihara, Y.;Fukumoto, Y.; Chatani, N., Nickel-Catalyzed Chelation-AssistedTransformations Involving Ortho C–H Bond Activation: Regioselective OxidativeCycloaddition of Aromatic Amides to Alkynes. Journal of the American ChemicalSociety 2011, 133, 14952-14955. d) Rouquet, G.; Chatani, N., Ruthenium-catalyzed ortho-C–H bond alkylation of aromatic amides with α,β-unsaturatedketones via bidentate-chelation assistance. Chemical Science 2013, 4, 2201-2208. e). Aihara, Y.; Chatani, N., Nickel-Catalyzed Direct Arylation of C(sp3)–H Bonds in Aliphatic Amides via Bidentate-Chelation Assistance. Journalof the American Chemical Society 2014, 136, 898-901. f) Yokota, A.; Aihara,Y.; Chatani, N., Nickel(II)-Catalyzed Direct Arylation of C–H Bonds inAromatic Amides Containing an 8-Aminoquinoline Moiety as a Directing Group.The Journal of Organic Chemistry 2014, 79, 11922-11932.
5 a) Page, P. C. B.; Klair, S. S.; Rosenthal, S. Synthesis andChemistry of Acyl Silanes. Chem. Soc. Rev. 1990, 19, 147. b) Zhang, H.-J.;Priebbenow, D. L.; Bolm, C. Acylsilanes: Valuable Organosilicon Reagents inOrganic Synthesis. Chem. Soc. Rev. 2013, 42, 8540. c) Feng, J.-J.; Oestreich,M. Tertiary α-Silyl Alcohols by Diastereoselective Coupling of 1,3-Dienes andAcylsilanes Initiated by Enantioselective Copper-Catalyzed Borylation. Angew. Chem., Int. Ed. 2019, 58, 8211. d) Obora, Y.; Ogawa, Y.; Imai, Y.; Kawamura,T.; Tsuji, Y. Palladium Complex Catalyzed Acylation of Allylic Esters withAcylsilanes. J. Am. Chem. Soc. 2001, 123, 10489. (b) Mattson, A. E.;Bharadwaj, A. R.; Scheidt, K. A. The Thiazolium-Catalyzed Sila-StetterReaction: Conjugate Addition of Acylsilanes to Unsaturated Esters andKetones. J. Am. Chem. Soc. 2004, 126, 2314. e) Ye, J.-H.; Quach, L.;Paulisch, T.; Glorius, F. Visible-Light-Induced, Metal-Free Carbene Insertioninto B−H Bonds between Acylsilanes and Pinacolborane. J. Am. Chem. Soc. 2019,141,16227. f) Lu, P.; Feng, C.; Loh, T.-P. Divergent Functionalization ofIndoles with Acryloyl Silanes via Rhodium-Catalyzed C−H Activation. Org. Lett. 2015, 17, 3210. g) Priebbenow, D. L. Insights into the Stability ofSiloxy Carbene Intermediates and Their Corresponding Oxocarbenium Ions. J. Org. Chem. 2019, 84, 11813。
Claims (4)
1.一种铑催化的碳氢活化反应合成酰基硅取代的异吲哚-1-酮类似物的方法，其特征在于在过渡金属铑催化剂、添加剂的作用下，以N-取代苯甲酰胺的酰胺为导向基团，α,β-不饱和酰基硅作为偶联试剂构建酰基硅取代基团，合成酰基硅取代的异吲哚-1-酮类似物，其化学反应式为：
其中，
所述的过渡金属铑催化剂为二氯（五甲基环戊二烯基）合铑（Ⅲ）、(二(六氟锑酸)三乙腈(五甲基环戊二烯基)铑(III))中的一种；
R1为氢、甲基、甲氧基、硝基、卤素中的一种；
R2为苯基，甲基、甲氧基、硝基、卤素取代的苯基中的一种。
2.根据权利要求1所述合成酰基硅取代的异吲哚-1-酮类似物的方法，其特征在于采用如下制备步骤：
在氩气保护下，在洁净的耐压瓶反应器中依次加入N-取代苯甲酰胺、α,β-不饱和酰基硅、过渡金属铑催化剂、添加剂和溶剂，放入100℃油浴中反应36h；
反应结束后，减压除去溶剂，用硅胶柱层析纯化得到产品。
3.根据权利要求2所述的制备方法，其特征在于溶剂为乙腈、四氢呋喃、1,2-二氯乙烷、甲苯、丙酮的一种；
添加剂为碳酸银、乙酸银、醋酸铜、一水合醋酸铜的一种。
4.根据权利要求2所述的制备方法，步骤中N-取代苯甲酰胺 : α,β-不饱和酰基硅:过渡金属铑催化剂:添加剂的摩尔比为1 : (2.0-4.0) : (0.05-0.1) : (1.5-2.5)。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110551139.5A CN113201006B (zh) | 2021-05-20 | 2021-05-20 | 一种铑催化的碳氢活化反应合成酰基硅取代的异吲哚-1-酮类似物的方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110551139.5A CN113201006B (zh) | 2021-05-20 | 2021-05-20 | 一种铑催化的碳氢活化反应合成酰基硅取代的异吲哚-1-酮类似物的方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113201006A CN113201006A (zh) | 2021-08-03 |
| CN113201006B true CN113201006B (zh) | 2022-05-17 |
Family
ID=77032168
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110551139.5A Expired - Fee Related CN113201006B (zh) | 2021-05-20 | 2021-05-20 | 一种铑催化的碳氢活化反应合成酰基硅取代的异吲哚-1-酮类似物的方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113201006B (zh) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113292477B (zh) * | 2021-06-01 | 2023-06-02 | 四川大学 | 一种铱催化的碳氢活化反应合成异吲哚-1-酮类化合物的方法 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107840819B (zh) * | 2017-12-06 | 2020-10-30 | 常州大学 | 一种多取代异吲哚啉酮衍生物的合成方法 |
| CN109485647B (zh) * | 2018-11-28 | 2021-04-13 | 浙江师范大学 | 一种抗焦虑药物帕戈隆或帕秦克隆的制备方法 |
| CN111533764B (zh) * | 2020-05-12 | 2023-06-06 | 杭州师范大学 | 一种利用多米诺反应制备硅氧基茚衍生物的方法 |
-
2021
- 2021-05-20 CN CN202110551139.5A patent/CN113201006B/zh not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN113201006A (zh) | 2021-08-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kopping et al. | Tris (trimethylsilyl) silane: an efficient hydrosilylating agent of alkenes and alkynes | |
| US20100076210A1 (en) | Method for producing a ruthenium complex | |
| Murakami et al. | A Study of the Stereochemical Course of β‐Oxygen Elimination with a Rhodium (I) Complex | |
| CN113201006B (zh) | 一种铑催化的碳氢活化反应合成酰基硅取代的异吲哚-1-酮类似物的方法 | |
| Zhao et al. | Nickel‐Catalyzed Intermolecular [3+ 2+ 2] and [2+ 2+ 2] Cocyclizations of Bicyclopropylidene and Alkynes | |
| CN109265386B (zh) | 一种通过c-h活化合成3-酰基化吲哚衍生物的新方法 | |
| EP2258707B1 (en) | Ruthenium silyl-arene complexes, and method for production thereof | |
| WO2005007662A2 (en) | Biphosphine ruthenium complexes with chiral diamine ligande as catalysts | |
| CN111099986B (zh) | 氢化反应方法 | |
| US5591854A (en) | Enantioselective synthesis of seven-membered carbocycles and tropanes | |
| Bolm et al. | A novel asymmetric synthesis of highly enantiomerically enriched norbornane-type diamine derivatives | |
| Crotti et al. | Rhodium-catalyzed enantioselective desymmetrization of bicyclic hydrazines with alkynylboronic esters | |
| EP2607353B1 (fr) | "Nouveau procédé de synthèse de l'ivabradine et de ses sels d'addition à un acide pharmaceutiquement acceptable" | |
| JP3780218B2 (ja) | 新規キラル銅触媒とそれを用いたｎ−アシル化アミノ酸誘導体の製造方法 | |
| CN113292477B (zh) | 一种铱催化的碳氢活化反应合成异吲哚-1-酮类化合物的方法 | |
| JP3738225B2 (ja) | 新規キラル銅触媒とそれを用いたｎ−アシル化アミノ酸誘導体の製造方法 | |
| JP7168161B2 (ja) | ヘテロール多量体の製造方法 | |
| CN110294772B (zh) | 一种2-烷基硅-苯甲酰胺类化合物及其合成方法 | |
| CN111018771B (zh) | 一种合成3-(2-氰基乙烯基)吲哚衍生物的方法 | |
| Hanzawa et al. | Rh (I)-catalyzed conjugate addition of alkenylzirconocene chloride: stereoselective formation of carbocycles through cascade reaction | |
| WO2008030840A2 (en) | Synthesis of sphingosines and their derivatives | |
| JP4112110B2 (ja) | アセチレン類とイソシアネート類との反応によるα，β−不飽和カルボキサミド類の製造方法 | |
| Xu et al. | Synthesis of New Chiral [2‐(1‐Hydroxyalkyl) pyrrolidino] methyl‐ferrocenes and Application to the Catalytic Asymmetric Addition of Diethylzinc to Arylaldehydes | |
| JP2004526741A (ja) | キラリティーが高められたシクロプロパンの生成方法 | |
| JP5039271B2 (ja) | ４−（トリアルキルシリルエチニル）フェナントレン誘導体 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20220517 |