Enantioselective Silylation of Simple Alcohols by Catalyst-Controlled Dehydrogenative Si-O Coupling
催化剂控制的脱氢 Si-O 偶联对简单醇进行对映选择性硅烷化
基本信息
- 批准号:388204995
- 负责人:
- 金额:--
- 依托单位:
- 依托单位国家:德国
- 项目类别:Research Grants
- 财政年份:2017
- 资助国家:德国
- 起止时间:2016-12-31 至 2021-12-31
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
Non-enzymatic kinetic resolution (KR) of alcohols through silylation rapidly established itself as an alternative to the common acylation in the last ten years. Substoichiometric amounts of chiral imidazole-type bases together with chlorosilanes enabled the KR and the related desymmetrization of a broad range of 1,2- and 1,3-diol motifs. Attempts to resolve monools, i.e., simple secondary or even tertiary alcohols, have only been met with limited success so far. The field was recently further advanced by the identification of chiral Brønsted acids as catalysts, and one of them, for the first time, allowed for the KR of unfunctionalized alcohols using hexamethyldisilazane as silylation reagent. Our approach to stereoselective alcohol silylation is based on transition-metal-catalyzed silicon-oxygen coupling of alcohols and hydrosilanes, liberating dihydrogen as the sole waste. Both reagent- and catalyst-controlled KRs were developed by us a few years ago but high selectivity factors were only achieved with donor-functionalized and as such biased alcohols. After considerable experimentation, we found a powerful catalyst/hydrosilane combination that mediates the dehydrogenative coupling between simple alcohol and commercially available hydrosilanes with high efficiency. The project aims at putting this new method on a sound basis, including broad substrate scope and extension to desymmetrization reactions.
在过去的十年里,通过硅基化的醇的非酶动力学分解(KR)迅速确立了自己作为一种替代常见的酰化。亚化学计量量的手性咪唑型碱基与氯硅烷一起使KR和相关的1,2-和1,3-二醇基序的脱对称成为可能。迄今为止,试图解决单醇,即简单的仲醇甚至叔醇,只取得了有限的成功。最近,手性Brønsted酸作为催化剂的鉴定进一步推进了这一领域的发展,其中一种催化剂首次允许以六甲基二矽氮烷作为硅基化试剂的非官能化醇的KR。我们的立体选择性醇硅基化方法是基于过渡金属催化的醇和氢硅烷的硅氧偶联,释放二氢作为唯一的废物。试剂控制和催化剂控制的KRs在几年前就被我们开发出来了,但高选择性因子只在供体功能化和偏倚醇上实现。经过大量的实验,我们发现了一种强大的催化剂/氢硅烷组合,它可以高效地介导简单醇和市售氢硅烷之间的脱氢偶联。该项目的目的是使这种新方法有一个良好的基础,包括广泛的底物范围和扩展到不对称反应。
项目成果
期刊论文数量(7)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
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Professor Dr. Martin Oestreich其他文献
Professor Dr. Martin Oestreich的其他文献
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{{ truncateString('Professor Dr. Martin Oestreich', 18)}}的其他基金
Elucidation of the Reaction Mechanisms of Hydrosilylations with Cationic Transition-Metal Catalysts
阳离子过渡金属催化剂氢化硅烷化反应机理的阐明
- 批准号:
427411484 - 财政年份:2019
- 资助金额:
-- - 项目类别:
Research Grants
Transition-Metal-Free Transfer Hydrohalogenation
无过渡金属转移氢卤化
- 批准号:
405628012 - 财政年份:2018
- 资助金额:
-- - 项目类别:
Research Grants
Ionic and Radical Cross-Couplings for Carbon-Silicon Bond Formation
碳-硅键形成的离子和自由基交叉偶联
- 批准号:
388910461 - 财政年份:2017
- 资助金额:
-- - 项目类别:
Research Grants
Chiral Sulfur-Stabilized Silicon Cations as Lewis Acids for Enantioselective Diels-Alder Reactions
手性硫稳定硅阳离子作为路易斯酸用于对映选择性狄尔斯-阿尔德反应
- 批准号:
287280002 - 财政年份:2015
- 资助金额:
-- - 项目类别:
Research Grants
Catalytic enantioselective hydrosilylation of pyridines and benzannulated congeners
吡啶和苯环化同系物的催化对映选择性氢化硅烷化
- 批准号:
250883966 - 财政年份:2014
- 资助金额:
-- - 项目类别:
Research Grants
3-Silylated Cyclohexa-1,4-dienes as Surrogates for Gaseous and Harmful Hydrosilanes in Lewis-Acid Catalysis
3-硅烷化环六-1,4-二烯作为路易斯酸催化中气态和有害氢硅烷的替代品
- 批准号:
255836950 - 财政年份:2014
- 资助金额:
-- - 项目类别:
Research Grants
Erzeugung und Charakterisierung neuartiger übergangsmetallstabilisierter Silyliumionen
新型过渡金属稳定硅离子的生成和表征
- 批准号:
223669596 - 财政年份:2012
- 资助金额:
-- - 项目类别:
Research Grants
Kooperative Si-H-Bindungsaktivierung: Erzeugung potenter Siliciumelektrophile für die katalytische C(sp3)-F-Bindungsaktivierung
协同 Si-H 键活化:生成有效的硅亲电子试剂,用于催化 C(sp3)-F 键活化
- 批准号:
218347001 - 财政年份:2012
- 资助金额:
-- - 项目类别:
Research Grants
Zinc Atom Transfer-Based Silylzincation of Alkynes
基于锌原子转移的炔烃的甲硅烷基锌化
- 批准号:
208581294 - 财政年份:2012
- 资助金额:
-- - 项目类别:
Research Grants
Heterolytische Aktivierung von H-H- und Si-H-Bindungen durch Lewis-Säure-/Lewis-Base-Paare in (asymmetrischen) metallfreien Reduktionen
在(不对称)无金属还原中路易斯酸/路易斯碱对对 H-H 和 Si-H 键的杂解活化
- 批准号:
105045747 - 财政年份:2008
- 资助金额:
-- - 项目类别:
Research Grants
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Catalytic Silylation of Aryl C-H Bonds with Earth Abundant Metal Catalysts
地球丰富的金属催化剂催化芳基 C-H 键的硅烷化
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RUI: Diruthenium Catalysts for the Silylation of Carbon-Hydrogen bonds
RUI:用于碳-氢键硅烷化的二钌催化剂
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Development of Catalytic Silylation Reaction of Nitrogen-containing Aromatic Compounds via C-H Bond Activation
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- 批准号:
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Silicone elastomers through reductive silylation of acrylates.
通过丙烯酸酯的还原硅烷化形成有机硅弹性体。
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480575-2015 - 财政年份:2015
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RUI: Reaction Acceleration, Mediation, and Catalysis by In Situ Silylation
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CAREER:Asymmetric Silylation of Secondary Alcohols and Mechanistic Investigations
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Transition Metal-Catalyzed, Asymmetric Allylic Borylation and Silylation
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7616725 - 财政年份:2008
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