Diastereodivergent Aldol‐Type Coupling of Alkoxyallenes with Pentafluorophenyl Esters Enabled by Synergistic Palladium/Chiral Lewis Base Catalysis

Angewandte Chemie, Journal Year: 2022, Volume and Issue: 134(33)

Published: June 17, 2022

Abstract As a fundamental and synthetically useful C−C bond formation reaction, the aldol reaction is one of most versatile transformations in organic synthesis. However, despite extensive research on asymmetric versions unified method for stereoselective access to complementary syn anti diastereomeric products remains be developed. In this study, we developed synergistic palladium/chiral Lewis base system that overcomes inherent diastereoselectivity bias reactions and, as result, allowed us achieve first diastereodivergent coupling alkoxyallenes with pentafluorophenol esters. Computational studies suggest mechanism involving an intermolecular protonative hydropalladation pathway rather than palladium‐hydride migratory insertion pathway. The origin stereochemistry catalysis rationalized by DFT calculations.

Language: Английский

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Stereodivergent Desymmetrization of Simple Dicarboxylates via Branch‐Selective Pd/Cu Catalyzed Allylic Substitution

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 28(24)

Published: March 9, 2022

Asymmetric desymmetrization has been demonstrated to be a powerful strategy for building stereocenters in asymmetric synthesis. Herein, Pd/Cu catalyzed reaction with simple geminal dicarboxylate is reported. A wide scope of imino esters bearing an aryl or heteroaromatic group were compatible this bimetallic catalytic system. The reactions proceeded smoothly, giving the desired products good yields high excellent regio-, diastereo-, and enantioselectivity (up 20 : 1 branched:linear, >20 dr, >99 % ee). Notably, favored branched selectivity, which unusual Pd-catalyzed allylic alkylation reaction. In addition, standard product could easily transformed other valuable molecules such as chiral alcohols, carbamates, organic boron compounds. Furthermore, DFT calculations conducted explain origin selectivity.

Language: Английский

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Stereodivergent Construction of 1,4‐Nonadjacent Stereocenters via Hydroalkylation of Racemic Allylic Alcohols Enabled by Copper/Ruthenium Relay Catalysis

Angewandte Chemie, Journal Year: 2022, Volume and Issue: 134(36)

Published: June 28, 2022

Abstract An unprecedented hydroalkylation of racemic allylic alcohols and ketimine esters enabled by Cu/Ru relay catalysis has been developed via merging the ruthenium‐catalyzed asymmetric borrowing‐hydrogen reaction with a copper‐catalyzed Michael addition in one‐pot procedure. The current method enables efficient preparation highly functionalized δ‐hydroxyesters bearing 1,4‐nonadjacent stereocenters good yields high levels diastereoselectivity excellent enantioselectivity under mild conditions. full complement four stereoisomers products could be readily accessed orthogonal permutations two chiral metal catalysts. work highlights power for stereodivergent construction that were otherwise inaccessible.

Language: Английский

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Synthesis, antiproliferative evaluation and in silico studies of a novel steroidal spiro morpholinone

Steroids, Journal Year: 2023, Volume and Issue: 192, P. 109173 - 109173

Published: Jan. 6, 2023

Language: Английский

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Palladium‐Catalyzed Asymmetric Decarboxylative Addition of β‐Keto Acids to Heteroatom‐Substituted Allenes

Angewandte Chemie, Journal Year: 2021, Volume and Issue: 133(41), P. 22340 - 22345

Published: July 15, 2021

Abstract The Pd‐catalyzed asymmetric addition reaction of β‐keto acids to heteroatom‐substituted allene is reported. This generates β‐substituted ketones in an manner through a branch‐selective decarboxylative allylation pathway. accommodates various alkoxyallenes as well amidoallenes.

Language: Английский

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