Asymmetric Synthesis of Isoindolones by Chiral Cyclopentadienyl‐Rhodium(III)‐Catalyzed CH Functionalizations

Angewandte Chemie International Edition, Journal Year: 2014, Volume and Issue: 53(30), P. 7896 - 7899

Published: June 10, 2014

Directed Cp*Rh(III)-catalyzed carbon-hydrogen (C-H) bond functionalizations have evolved as a powerful strategy for the construction of heterocycles. Despite their high value, development related asymmetric reactions is largely lagging behind due to limited availability robust and tunable chiral cyclopentadienyl ligands. Rhodium complexes comprising Cp ligand with an atropchiral biaryl backbone enables synthesis isoindolones from arylhydroxamates weakly alkyl donor/acceptor diazo derivatives one-carbon component under mild conditions. The complex guides substrates double facial selectivity yielding in good yields excellent enantioselectivities.

Language: Английский

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Dehydrative Direct CH Allylation with Allylic Alcohols under [Cp*Co^III] Catalysis

Angewandte Chemie International Edition, Journal Year: 2015, Volume and Issue: 54(34), P. 9944 - 9947

Published: July 1, 2015

Abstract The unique reactivity of [Cp*Co III ] over [Cp*Rh was demonstrated. A cationic catalyst promoted direct dehydrative CH allylation with non‐activated allyl alcohols, thus giving C2‐allylated indoles, pyrrole, and phenyl‐pyrazole in good yields, while analogous catalysts were not effective. high γ‐selectivity C2‐selectivity indicated that the reaction proceeded by directing‐group‐assisted metalation. DFT calculations suggested γ‐selective substitution metalation insertion a CC double bond, subsequent β‐hydroxide elimination. favored elimination β‐hydride

Language: Английский

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High‐Valent‐Cobalt‐Catalyzed C−H Functionalization Based on Concerted Metalation–Deprotonation and Single‐Electron‐Transfer Mechanisms

ChemCatChem, Journal Year: 2016, Volume and Issue: 8(7), P. 1242 - 1263

Published: March 23, 2016

Abstract C−H functionalization has been established as a powerful strategy for the commercial construction of organic molecules. This review encompasses most recent advances in activation catalyzed by earth‐abundant cobalt complexes, involving two types fundamental reaction paths, that is, concerted metalation–deprotonation (CMD) path associated with non‐oxidative and intermolecular single‐electron‐transfer (SET) path. Transformations high‐valent based on mechanisms used syntheses, including those C−C C−X (X=O N) bond formation, are herein presented.

Language: Английский

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Mild Rhodium(III)‐Catalyzed Direct CH Allylation of Arenes with Allyl Carbonates

Angewandte Chemie International Edition, Journal Year: 2013, Volume and Issue: 52(20), P. 5386 - 5389

Published: April 10, 2013

All(yl) possible! A rhodium(III)-catalyzed intermolecular direct CH allylation reaction utilizing readily accessible allyl carbonates was developed. This method allows the of electron-neutral arenes, providing complete γ-selectivity, high isomeric ratio, good substrate scope, and excellent functional group compatibility. As a service to our authors readers, this journal provides supporting information supplied by authors. Such materials are peer reviewed may be re-organized for online delivery, but not copy-edited or typeset. Technical support issues arising from (other than missing files) should addressed Please note: The publisher is responsible content functionality any Any queries content) directed corresponding author article.

Language: Английский

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Transition Metal‐Catalyzed Enantioselective C−H Functionalization via Chiral Transient Directing Group Strategies

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(45), P. 19773 - 19786

Published: July 20, 2020

Abstract Transition metal‐catalyzed enantioselective functionalization of C−H bond, the most abundant functionality in organic molecules, has emerged as an expedient synthetic approach to streamline synthesis complex chiral molecules. Despite significant progress, traditional directing group‐enabled strategies require additional steps for installation and removal groups from target molecule. The recently developed asymmetric using transient ( c TDGs) offers a promising alternative that can circumvent this obstacle therefore simplify process. In Minireview, we briefly discuss advent recent advances emerging concept, with emphasis on discussing creation various stereogenic centers developments TDGs. Applications natural product ligand derivatizations are also discussed. We hope Minireview will highlight great potential strategy help inspire further endeavors.

Language: Английский

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