Zhichao Jin

Bio: Zhichao Jin is an academic researcher from Guizhou University. The author has contributed to research in topics: Carbene & Enantioselective synthesis. The author has an hindex of 19, co-authored 65 publications receiving 1077 citations. Previous affiliations of Zhichao Jin include Nanyang Technological University & University of Pavia.

Carbon–carbon bond activation of cyclobutenones enabled by the addition of chiral organocatalyst to ketone

Abstract: The activation of carbon–carbon (C–C) bonds is an effective strategy in building functional molecules. The C–C bond activation is typically accomplished via metal catalysis, with which high levels of enantioselectivity are difficult to achieve due to high reactivity of metal catalysts and the metal-bound intermediates. It remains largely unexplored to use organocatalysis for C–C bond activation. Here we describe an organocatalytic activation of C–C bonds through the addition of an NHC to a ketone moiety that initiates a C–C single bond cleavage as a key step to generate an NHC-bound intermediate for chemo- and stereo-selective reactions. This reaction constitutes an asymmetric functionalization of cyclobutenones using organocatalysts via a C–C bond activation process. Structurally diverse and multicyclic compounds could be obtained with high optical purities via an atom and redox economic process.

Carbene-Catalyzed Asymmetric Construction of Atropisomers.

Abstract: Atropisomeric molecules have found proven applications and promising potentials in chemistry and medicines. The design of N-heterocyclic carbene (NHC)-catalyzed reactions in constructing atropisomerically enriched molecules emerged as an important research topic in recent years. These reactions include kinetic resolutions, asymmetric desymmetrizations, central-to-axial chirality conversions, and cycloadditions. This review evaluates and summarizes the progress on NHC organic catalysis for access to atropisomers, and briefly states our personal perspectives on the future advancement of this direction. NHC catalysis has provided rich and unique reaction modes with numerous success in asymmetric synthesis of central chiral molecules. It is expected that similar success can also be achieved in developing NHC catalysis to prepare atropisomeric molecules, including those not easily accessible with other methods. Readers in the broadly defined community of chemistry shall find this review as a valuable source for information and hopefully inspirations.

β‐Functionalization of Carboxylic Anhydrides with β‐Alkyl Substituents through Carbene Organocatalysis

Abstract: The first NHC-catalyzed functionalization of carboxylic anhydrides is described. In this reaction, the β carbon behaves as a nucleophilic carbon and undergoes asymmetric reactions with electrophiles. Anhydrides with challenging β-alkyl substituents work effectively.

Organocatalysis in Inert C–H Bond Functionalization

Abstract: As two coexisting and fast-growing research fields in modern synthetic chemistry, the merging of organocatalysis and C–H bond functionalization is well foreseeable, and the joint force along this line has been demonstrated to be a powerful approach in making inert C–H bond functionalization more viable, predictable, and selective. In this review, we provide a comprehensive summary of organocatalysis in inert C–H bond functionalization over the past two decades. The review is arranged by types of inert C–H bonds including alkane C–H, arene C–H, and vinyl C–H as well as those activated benzylic C–H, allylic C–H, and C–H bonds alpha to the heteroatom such as nitrogen and oxygen. In each section, the discussion is classified by the explicit organocatalytic mode involved.

Recent advances in employing homoenolates generated by N-heterocyclic carbene (NHC) catalysis in carbon–carbon bond-forming reactions

Abstract: The use of NHCs for generating homoenolate species has gained widespread popularity in recent years. A number of highly stereoselective processes of NHC-homoenolates have emerged. Homoenolate reactions have also been employed as key steps in the total synthesis of a number of natural products. The use of compatible co-catalysts, improved NHC-catalyst design and the use of novel precursors for homoenolate generation are among the major developments in this area that were disclosed recently. This tutorial review organises and presents the advancements in this rapidly growing area of catalysis and in the process updates a previous account published in 2011 in this journal.

Phosphine-Catalyzed Asymmetric Organic Reactions.

Abstract: Asymmetric phosphine catalysis showcasing remarkable progress over the past two decades has emerged as a key synthetic platform for the creation of molecular frameworks encountered in medicinal chemistry and materials science. Different types of novel chiral phosphine catalysts have been developed and employed in cornucopias of organic transformations, such as annulation, addition, Morita–Baylis–Hillman, and Rauhut–Currier reactions, among others. This review summarizes all of the literature examples from late 1990s to the end of 2017, alongside their mechanistic insights whenever possible, with a very aim to trigger more intensive research in the future to render asymmetric phosphine catalysis one of the most common and reliable tools to organic chemists.