• 文献检索
  • 文档翻译
  • 深度研究
  • 学术资讯
  • Suppr Zotero 插件Zotero 插件
  • 邀请有礼
  • 套餐&价格
  • 历史记录
应用&插件
Suppr Zotero 插件Zotero 插件浏览器插件Mac 客户端Windows 客户端微信小程序
定价
高级版会员购买积分包购买API积分包
服务
文献检索文档翻译深度研究API 文档MCP 服务
关于我们
关于 Suppr公司介绍联系我们用户协议隐私条款
关注我们

Suppr 超能文献

核心技术专利：CN118964589B侵权必究
粤ICP备2023148730 号-1Suppr @ 2026

文献检索

告别复杂PubMed语法，用中文像聊天一样搜索，搜遍4000万医学文献。AI智能推荐，让科研检索更轻松。

立即免费搜索

文件翻译

保留排版，准确专业，支持PDF/Word/PPT等文件格式，支持 12+语言互译。

免费翻译文档

深度研究

AI帮你快速写综述，25分钟生成高质量综述，智能提取关键信息，辅助科研写作。

立即免费体验

NHC-铜催化的硅基对无环和环状二烯酮及二烯酸酯的共轭加成反应。含羰基烯丙基硅烷的高效位点、非对映和对映选择性合成。

NHC-Cu-Catalyzed Silyl Conjugate Additions to Acyclic and Cyclic Dienones and Dienoates. Efficient Site-, Diastereo- and Enantioselective Synthesis of Carbonyl-Containing Allylsilanes.

作者信息

Lee Kang-Sang, Wu Hao, Haeffner Fredrik, Hoveyda Amir H

机构信息

Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467.

出版信息

Organometallics. 2012 Nov 26;31(22):7823-7826. doi: 10.1021/om300790t. Epub 2012 Sep 19.

DOI:10.1021/om300790t
PMID:23264716
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC3524594/
Abstract

Efficient and highly diastereo- and enantioselective conjugate additions of phenyldimethylsilyl units to acyclic and cyclic dienones and dienoates are disclosed. The C-Si bond forming reactions are catalyzed by 2.0-2.5 mol % of a copper complex of a chiral monodentate N-heterocyclic carbene; the requisite reagent, PhMe(2)Si-B(pin), is commercially available or can be easily prepared. Transformations generate allylsilanes in up to 98% yield and >99:1 enantiomeric ratio, and proceed with complete 1,4-selectivity, unless the dienone or dienoate carries a trisubstituted alkene conjugated to the carbonyl group; in the latter cases, 1,6-addition products are obtained exclusively and in up to >98% Z selectivity.

摘要

公开了苯基二甲基硅基单元与无环和环状二烯酮及二烯酸酯的高效、高非对映和对映选择性共轭加成反应。形成C-Si键的反应由2.0 - 2.5 mol%的手性单齿N-杂环卡宾铜配合物催化；所需试剂PhMe(2)Si-B(pin)可商购或易于制备。反应生成的烯丙基硅烷产率高达98%，对映体比例>99:1，且具有完全的1,4-选择性，除非二烯酮或二烯酸酯带有与羰基共轭的三取代烯烃；在后一种情况下，仅得到1,6-加成产物，且Z选择性高达>98%。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ed2b/3524594/e0a19279d149/nihms-409246-f0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ed2b/3524594/31b2c447f392/nihms-409246-f0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ed2b/3524594/5ee64137891a/nihms-409246-f0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ed2b/3524594/e0a19279d149/nihms-409246-f0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ed2b/3524594/31b2c447f392/nihms-409246-f0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ed2b/3524594/5ee64137891a/nihms-409246-f0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ed2b/3524594/e0a19279d149/nihms-409246-f0005.jpg

相似文献

1
NHC-Cu-Catalyzed Silyl Conjugate Additions to Acyclic and Cyclic Dienones and Dienoates. Efficient Site-, Diastereo- and Enantioselective Synthesis of Carbonyl-Containing Allylsilanes.NHC-铜催化的硅基对无环和环状二烯酮及二烯酸酯的共轭加成反应。含羰基烯丙基硅烷的高效位点、非对映和对映选择性合成。
Organometallics. 2012 Nov 26;31(22):7823-7826. doi: 10.1021/om300790t. Epub 2012 Sep 19.
2
Enantioselective conjugate silyl additions to cyclic and acyclic unsaturated carbonyls catalyzed by Cu complexes of chiral N-heterocyclic carbenes.手性氮杂环卡宾铜配合物催化的环状和非环状不饱和羰基化合物的对映选择性共轭硅烷加成反应。
J Am Chem Soc. 2010 Mar 10;132(9):2898-900. doi: 10.1021/ja910989n.
3
A broadly applicable NHC-Cu-catalyzed approach for efficient, site-, and enantioselective coupling of readily accessible (pinacolato)alkenylboron compounds to allylic phosphates and applications to natural product synthesis.一种广泛适用的 NHC-Cu 催化方法，用于高效、位点和对映选择性地偶联易得的（频哪醇基）烯基硼化合物与烯丙基磷酸酯，并应用于天然产物合成。
J Am Chem Soc. 2014 Feb 5;136(5):2149-61. doi: 10.1021/ja4126565. Epub 2014 Jan 28.
4
Metal-free catalytic C-Si bond formation in an aqueous medium. Enantioselective NHC-catalyzed silyl conjugate additions to cyclic and acyclic α,β-unsaturated carbonyls.无金属催化的 C-Si 键在水相中的形成。手性 NHC 催化的硅基共轭加成到环状和非环状的 α,β-不饱和羰基化合物。
J Am Chem Soc. 2011 May 25;133(20):7712-5. doi: 10.1021/ja203031a. Epub 2011 Apr 27.
5
Exceptionally E- and β-selective NHC-Cu-catalyzed proto-silyl additions to terminal alkynes and site- and enantioselective proto-boryl additions to the resulting vinylsilanes: synthesis of enantiomerically enriched vicinal and geminal borosilanes.异常的 E- 和 β-选择性 NHC-Cu 催化的末端炔烃的原硅烷基加成以及生成的乙烯基硅烷的位点和对映选择性原硼酸酯加成：对映体富集的偕二硼硅烷和连二硼硅烷的合成。
Chemistry. 2013 Feb 25;19(9):3204-14. doi: 10.1002/chem.201203803. Epub 2013 Jan 16.
6
S2″-Selective and Enantioselective Substitution with Unsaturated Organoboron Compounds and Catalyzed by a Sulfonate-Containing NHC-Cu Complex.S2″-不饱和有机硼化合物的选择性和对映选择性取代反应及含磺酸酯基的 NHC-Cu 配合物的催化作用。
J Am Chem Soc. 2018 Dec 5;140(48):16842-16854. doi: 10.1021/jacs.8b10885. Epub 2018 Nov 16.
7
Catalytic enantioselective 1,6-conjugate additions of propargyl and allyl groups.炔丙基和烯丙基的催化对映选择性1,6-共轭加成反应。
Nature. 2016 Sep 15;537(7620):387-393. doi: 10.1038/nature19063. Epub 2016 Aug 1.
8
Cu-catalyzed asymmetric conjugate additions of dialkyl- and diarylzinc reagents to acyclic beta-silyl-alpha,beta-unsaturated ketones. Synthesis of allylsilanes in high diastereo- and enantiomeric purity.铜催化二烷基锌和二芳基锌试剂对非环状β-硅基-α,β-不饱和酮的不对称共轭加成反应。高非对映体和对映体纯度烯丙基硅烷的合成。
Org Lett. 2007 Aug 2;9(16):3187-90. doi: 10.1021/ol071331k. Epub 2007 Jun 30.
9
Efficient boron-copper additions to aryl-substituted alkenes promoted by NHC-based catalysts. enantioselective Cu-catalyzed hydroboration reactions.NHC 基催化剂促进的芳基取代烯烃的高效硼铜加成反应。对映选择性 Cu 催化的硼氢化反应。
J Am Chem Soc. 2009 Mar 11;131(9):3160-1. doi: 10.1021/ja809382c.
10
Monodentate non-C(2)-symmetric chiral N-heterocyclic carbene complexes for enantioselective synthesis. Cu-catalyzed conjugate additions of aryl- and alkenylsilylfluorides to cyclic enones.用于对映选择性合成的单齿非C(2)对称手性N-杂环卡宾配合物。铜催化芳基和烯基甲硅烷基氟化物对环状烯酮的共轭加成反应。
J Org Chem. 2009 Jun 19;74(12):4455-62. doi: 10.1021/jo900589x.

引用本文的文献

1
The structures and reactivity of NHC-supported copper(i) triphenylgermyls.氮杂环卡宾负载的三苯基锗基铜（I）配合物的结构与反应活性
Chem Sci. 2023 Dec 1;15(2):584-593. doi: 10.1039/d3sc05862j. eCollection 2024 Jan 3.
2
Copper-Catalyzed Enantioselective Hydrosilylation of gem-Difluorocyclopropenes Leading to a Stereochemical Study of the Silylated gem-Difluorocyclopropanes.铜催化的对映选择性氢硅烷化 gem-二氟环丙烯，导致对甲硅烷基化 gem-二氟环丙烷的立体化学研究。
Chemistry. 2022 Jun 7;28(32):e202200657. doi: 10.1002/chem.202200657. Epub 2022 May 2.
3
Ruthenium(ii)-catalyzed regioselective 1,6-conjugate addition of umpolung aldehydes as carbanion equivalents.钌（II）催化的极性反转醛作为碳负离子等价物的区域选择性1,6-共轭加成反应。
Chem Sci. 2021 Nov 29;13(1):118-122. doi: 10.1039/d1sc03732c. eCollection 2021 Dec 22.
4
Recent advances in Cu-catalyzed C(sp)-Si and C(sp)-B bond formation.铜催化的C(sp)-Si和C(sp)-B键形成的最新进展。
Beilstein J Org Chem. 2020 Apr 15;16:691-737. doi: 10.3762/bjoc.16.67. eCollection 2020.
5
Iron-Catalyzed Asymmetric Hydrosilylation of Vinylcyclopropanes via Stereospecific C-C Bond Cleavage.通过立体特异性碳-碳键裂解实现铁催化的乙烯基环丙烷的不对称硅氢化反应
iScience. 2020 Apr 24;23(4):100985. doi: 10.1016/j.isci.2020.100985. Epub 2020 Mar 17.
6
Copper-Catalyzed Enantio- and Diastereoselective Addition of Silicon Nucleophiles to 3,3-Disubstituted Cyclopropenes.铜催化的硅亲核试剂对 3,3-二取代环丙烯的对映选择性和非对映选择性加成反应。
Chemistry. 2019 Nov 13;25(63):14304-14307. doi: 10.1002/chem.201904272. Epub 2019 Oct 22.
7
Synthesis of Enantioenriched Allylic Silanes via Nickel-Catalyzed Reductive Cross-Coupling.通过镍催化还原交叉偶联反应合成对映体富集的烯丙基硅烷。
J Am Chem Soc. 2018 Jan 10;140(1):139-142. doi: 10.1021/jacs.7b11707. Epub 2017 Dec 20.
8
Copper-catalyzed silylation of p-quinone methides: new entry to dibenzylic silanes.铜催化对醌甲基化物的硅氢化反应：二苄基硅烷的新合成方法
Chem Commun (Camb). 2015 Dec 28;51(100):17684-7. doi: 10.1039/c5cc06653k.
9
Mechanism of NHC-Catalyzed Conjugate Additions of Diboron and Borosilane Reagents to α,β-Unsaturated Carbonyl Compounds.NHC催化二硼试剂和硼硅烷试剂对α,β-不饱和羰基化合物进行共轭加成的机理
J Am Chem Soc. 2015 Aug 26;137(33):10585-602. doi: 10.1021/jacs.5b06745. Epub 2015 Aug 11.
10
Preparation of macrocyclic Z-enoates and (E,Z)- or (Z,E)-dienoates through catalytic stereoselective ring-closing metathesis.通过催化立体选择性闭环复分解反应制备大环Z-烯酸酯和（E，Z）-或（Z，E）-二烯酸酯。
J Am Chem Soc. 2014 Nov 26;136(47):16493-6. doi: 10.1021/ja510768c. Epub 2014 Nov 17.

本文引用的文献

1
Aminocatalytic enantioselective 1,6 additions of alkyl thiols to cyclic dienones: vinylogous iminium ion activation.手性氨基催化的烷基硫醇与环状二烯酮的 1,6 加成反应：烯胺离子的 vinylogous 活化。
Angew Chem Int Ed Engl. 2012 Jun 25;51(26):6439-42. doi: 10.1002/anie.201202392. Epub 2012 May 22.
2
Metal-free catalytic enantioselective C-B bond formation: (pinacolato)boron conjugate additions to α,β-unsaturated ketones, esters, Weinreb amides, and aldehydes promoted by chiral N-heterocyclic carbenes.无金属催化的对映选择性 C-B 键形成：手性 N-杂环卡宾促进的（频哪醇硼酸酯）硼与α,β-不饱和酮、酯、Weinreb 酰胺和醛的加成反应。
J Am Chem Soc. 2012 May 16;134(19):8277-85. doi: 10.1021/ja302929d. Epub 2012 May 4.
3
Metal-free catalytic C-Si bond formation in an aqueous medium. Enantioselective NHC-catalyzed silyl conjugate additions to cyclic and acyclic α,β-unsaturated carbonyls.无金属催化的 C-Si 键在水相中的形成。手性 NHC 催化的硅基共轭加成到环状和非环状的 α,β-不饱和羰基化合物。
J Am Chem Soc. 2011 May 25;133(20):7712-5. doi: 10.1021/ja203031a. Epub 2011 Apr 27.
4
Enantioselective synthesis of boron-substituted quaternary carbons by NHC-Cu-catalyzed boronate conjugate additions to unsaturated carboxylic esters, ketones, or thioesters.手性 NHC-Cu 催化硼酸盐与不饱和羧酸酯、酮或硫酯的共轭加成反应合成硼取代的季碳中心
J Am Chem Soc. 2010 Aug 11;132(31):10630-3. doi: 10.1021/ja104777u.
5
Iridium/chiral diene-catalyzed asymmetric 1,6-addition of arylboroxines to alpha,beta,gamma,delta-unsaturated carbonyl compounds.铱/手性二烯催化的芳基硼酸对α，β，γ，δ-不饱和羰基化合物的不对称 1,6-加成。
J Am Chem Soc. 2010 Jun 16;132(23):7872-3. doi: 10.1021/ja1034842.
6
Enantioselective conjugate silyl additions to cyclic and acyclic unsaturated carbonyls catalyzed by Cu complexes of chiral N-heterocyclic carbenes.手性氮杂环卡宾铜配合物催化的环状和非环状不饱和羰基化合物的对映选择性共轭硅烷加成反应。
J Am Chem Soc. 2010 Mar 10;132(9):2898-900. doi: 10.1021/ja910989n.
7
Monodentate non-C(2)-symmetric chiral N-heterocyclic carbene complexes for enantioselective synthesis. Cu-catalyzed conjugate additions of aryl- and alkenylsilylfluorides to cyclic enones.用于对映选择性合成的单齿非C(2)对称手性N-杂环卡宾配合物。铜催化芳基和烯基甲硅烷基氟化物对环状烯酮的共轭加成反应。
J Org Chem. 2009 Jun 19;74(12):4455-62. doi: 10.1021/jo900589x.
8
Efficient C-B bond formation promoted by N-heterocyclic carbenes: synthesis of tertiary and quaternary B-substituted carbons through metal-free catalytic boron conjugate additions to cyclic and acyclic alpha,beta-unsaturated carbonyls.氮杂环卡宾促进的高效C-B键形成：通过无金属催化硼对环状和非环状α,β-不饱和羰基的共轭加成合成叔碳和季碳取代的硼化物
J Am Chem Soc. 2009 Jun 3;131(21):7253-5. doi: 10.1021/ja902889s.
9
Regiodivergent 1,4 versus 1,6 asymmetric copper-catalyzed conjugate addition.区域发散性的1,4与1,6不对称铜催化共轭加成反应。
Angew Chem Int Ed Engl. 2008;47(47):9122-4. doi: 10.1002/anie.200803735.
10
Asymmetric synthesis of tertiary alcohols and alpha-tertiary amines via Cu-catalyzed C-C bond formation to ketones and ketimines.通过铜催化的碳-碳键形成反应合成酮和酮亚胺实现叔醇和α-叔胺的不对称合成。
Chem Rev. 2008 Aug;108(8):2853-73. doi: 10.1021/cr078340r. Epub 2008 Jun 21.