Rhodium-Catalyzed Allylation Reactions

Synthesis, Journal Year: 2019, Volume and Issue: 51(13), P. 2585 - 2631

Published: April 30, 2019

Rhodium-catalyzed allylation reactions are well known for their unique selectivity and reactivity due to the high memory effect of Rh as compared other metals. These involve substitution allylic rhodium intermediates with a diverse range different nucleophiles, leading C–C C–heteroatom bond formation. Modern organic chemists are, however, interested in atom-economical protocols under greener pathways following recent increased understanding mechanistic aspects Rh-catalyzed via hydrofunctionalization allenes or alkynes, great strides have made design development new protocols. In this article, we review field from its beginning current state. 1 Introduction 2 Rhodium-Catalyzed Allylic Substitution 3 Allylation Allenes 4 Alkynes 5 Dienes 6 by ARO Oxabicyclic Alkenes 7 Enantioselective Natural Product Drug Synthesis 8 Conclusion

Language: Английский

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Iridium‐Catalyzed Enantioselective Intermolecular Indole C2‐Allylation

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(19), P. 7598 - 7604

Published: Feb. 24, 2020

The enantioselective intermolecular C2-allylation of 3-substituted indoles is reported for the first time. This directing group-free approach relies on a chiral Ir-(P, olefin) complex and Mg(ClO4 )2 Lewis acid catalyst system to promote allylic substitution, providing C2-allylated products in typically high yields (40-99 %) enantioselectivities (83-99 % ee) with excellent regiocontrol. Experimental studies DFT calculations suggest that reaction proceeds via direct C2-allylation, rather than C3-allylation followed by situ migration. Steric congestion at indole-C3 position improved π-π stacking interactions have been identified as major contributors C2-selectivity.

Language: Английский

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Reducing Challenges in Organic Synthesis with Stereoselective Hydrogenation and Tandem Catalysis

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(18), P. 6724 - 6745

Published: April 23, 2021

Tandem catalysis enables the rapid construction of complex architectures from simple building blocks. This Perspective shares our interest in combining stereoselective hydrogenation with transformations such as isomerization, oxidation, and epimerization to solve diverse challenges. We highlight use tandem for preparing natural products prochiral blocks present involving transfer dynamic kinetic resolution. Finally, we underline recent breakthroughs opportunities asymmetric hydrogenation.

Language: Английский

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Cooperative Pd/Cu-catalyzed diastereodivergent coupling of allenamides and aldimine esters to access the Mannich-type motifs

Chem Catalysis, Journal Year: 2022, Volume and Issue: 2(6), P. 1428 - 1439

Published: May 4, 2022

Language: Английский

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Rhodium-Catalyzed Enantioselective Decarboxylative Alkynylation of Allenes with Arylpropiolic Acids

Organic Letters, Journal Year: 2018, Volume and Issue: 20(4), P. 1066 - 1069

Published: Feb. 5, 2018

A rhodium-catalyzed chemo-, regio-, and enantioselective intermolecular decarboxylative alkynylation of terminal allenes with arylpropiolic acids is reported. Employing a Rh(I)/(R)-Tol-BINAP catalytic system, branched allylic 1,4-enynes were obtained under mild conditions. The overall utility this protocol exemplified by broad functional group compatibility.

Language: Английский

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