Application of Bifunctional (Thio)ureas with Auxiliary in Asymmetric Organocatalysis
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（硫）脲、亲核活化基与辅助基构成的手性双功能（硫）脲催化剂,具有易于调控的结构和优异的催化性能,因而,双功能（硫）脲催化成为目前不对称有机催化的一个重要研究领域.各类活化基的引入显著影响了该类催化剂的催化性能,成为催化剂设计的主要考虑方向,获得了广泛关注.此外,合适辅助基的引入也可调控与优化催化性能,成为催化剂设计的一个重要补充方法.然而,到目前为止尚没有利用辅助基策略构建双功能（硫）脲催化剂的系统的综述.从非手性辅助基与手性辅助基角度综述了双功能（硫）脲催化剂的设计与构建以及这些催化剂在系列不对称有机催化研究中的应用,阐述了辅助基结构中的位阻、手性环境、电子效应、氢键给体等因素对催化性能的影响作用,并对其今后的发展进行了展望.Keywords:
Thio-
Abstract Enantioselective desymmetrization of prochiral 1,3‐cyclodiketones is the most convenient and highly desired transformation to access densely functionalized, enantiomerically enriched scaffolds with multiple chiral centers. In recent years, organocatalysis has made significant progress in this research area along with other traditional metal‐ or enzyme‐catalyzed reactions. This mini‐review provides an overview of the recent developments in the domain of organocatalytic enantioselective desymmetrization along with a brief discussion about future perspectives.
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Abstract Organocatalytic methods have achieved spectacular advancements for the preparation of chiral molecules in highly enantioenriched forms. The fast development of this field can mainly be attributed to the evolution of general and reliable activation modes. The discovery and identification of new activation modes are therefore highly desirable to push the boundaries of asymmetric reactions. In this Minireview, recent advances in enantioselective carbonyl catalysis, one useful subbranch of organocatalysis for the efficient activation of simple amines, will be summarized. With elegantly designed chiral aldehyde catalysts, highly enantioselective and efficient asymmetric reactions can be developed. Continued development of enantioselective carbonyl catalysis is expected in the future.
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The enantioselective desymmetrization is regarded as an effective strategy for producing chiral compounds from achiral substrates. The past decade saw the establishment of organocatalysis in organic synthesis and also organocatalytic desymmetrizations have emerged in recent years. In particular, bifunctional organocatalysts have shown the ability to promote enantioselective desymmetrizations enabling simultaneous covalent and/or non-covalent activations of the reagents. Many classes of prochiral and meso compounds were efficiently desymmetrized, being cyclic anhydrides ringopening and diols acylation the most widely employed transformations. The goal of this review is to give a comprehensive overview on the developed strategies in the field of the enantioselective desymmetrizations promoted by bifunctional organocatalysts. Keywords: Bifunctional activation, desymmetrization, enantioselectivity, meso compound, organocatalysis, prochiral substrate.
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Organic Synthesis
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Abstract Organocatalytic methods have achieved spectacular advancements for the preparation of chiral molecules in highly enantioenriched forms. The fast development of this field can mainly be attributed to the evolution of general and reliable activation modes. The discovery and identification of new activation modes are therefore highly desirable to push the boundaries of asymmetric reactions. In this Minireview, recent advances in enantioselective carbonyl catalysis, one useful subbranch of organocatalysis for the efficient activation of simple amines, will be summarized. With elegantly designed chiral aldehyde catalysts, highly enantioselective and efficient asymmetric reactions can be developed. Continued development of enantioselective carbonyl catalysis is expected in the future.
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Abstract Review: [138 refs.]
Thio-
Primary (astronomy)
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A novel bifunctional chiral Brønsted acid/base catalyst is reported. The authors applied the new catalyst 1 to the enantioselective desymmetrization of meso-anhydrides, and the products were obtained in good yields and high enantioselectivities (er up to 99:1). The synthetic utility of this methodology was demonstrated in the symmetric formal synthesis of (+)-grandisol.
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Brønsted–Lowry acid–base theory
Base (topology)
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Abstract Enantioselective organocatalysis by using N‐heterocyclic carbenes (NHCs) has emerged as a powerful strategy for the construction of complex chiral molecules. Recently, remarkable advances have been made in enantioselective NHC‐catalyzed reactions that involve diverse activation intermediates, such as Breslow intermediates, homoenolate intermediates, α,β‐unsaturated acylazoliums, azolium enolates, and azolium dienolates, which are generated by the nucleophilic addition of NHCs to aldehydes. Furthermore, NHC‐catalyzed reactions that proceed through non‐covalent bonding interactions have also been developed.
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Abstract Organocatalysis is widely used for the asymmetric synthesis of natural products and pharmaceuticals, and bifunctional organocatalysts are particularly effective for controlling stereochemistry. Here, we present an overview of natural products syntheses involving bifunctional catalysts bearing a hydrogen‐bonding donor moiety reported during the last five years.
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Abstract The α‐oxysulfonylation of ketones catalysed by enantioenriched iodoarenes using m CPBA as stoichiometric oxidant is reported to give useful synthetic intermediates in good yield and modest enantioselectivity. We believe this to be the first report of an enantioselective organocatalytic reaction involving hypervalent iodine reagents which should open up a new field for enantioselective organocatalysis of oxidation reactions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
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