Dynamic kinetic resolution of allylic sulfoxides by Rh-catalyzed hydrogenation: a combined theoretical and experimental mechanistic study

Journal of the American Chemical Society
Peter K DornanVy M Dong

Abstract

A dynamic kinetic resolution (DKR) of allylic sulfoxides has been demonstrated by combining the Mislow [2,3]-sigmatropic rearrangement with catalytic asymmetric hydrogenation. The efficiency of our DKR was optimized by using low pressures of hydrogen gas to decrease the rate of hydrogenation relative to the rate of sigmatropic rearrangement. Kinetic studies reveal that the rhodium complex acts as a dual-role catalyst and accelerates the substrate racemization while catalyzing olefin hydrogenation. Scrambling experiments and theoretical modeling support a novel mode of sulfoxide racemization which occurs via a rhodium π-allyl intermediate in polar solvents. In nonpolar solvents, however, the substrate racemization is primarily uncatalyzed. Computational studies suggest that the sulfoxide binds to rhodium via O-coordination throughout the catalytic cycle for hydrogenation.

References

Oct 24, 2001·The Journal of Organic Chemistry·Jérôme AmaudrutOlaf Wiest
Oct 25, 2001·The Journal of Organic Chemistry·Zhaohui S. ZhouDonald Hilvert
Apr 12, 2003·Organic Letters·Christopher J Pilkington, Antonio Zanotti-Gerosa
Sep 11, 2003·Chemical Reviews·Inmaculada Fernández, Noureddine Khiar
May 12, 2005·Journal of the American Chemical Society·Mark S ChenM Christina White
May 7, 2009·Journal of the American Chemical Society·Matthew M CoulterVy M Dong
Dec 23, 2010·Journal of the American Chemical Society·Sergiy LevinSarah E Reisman
Jan 12, 2011·Journal of the American Chemical Society·Hongli BaoUttam K Tambar
Nov 19, 2011·Chemistry : a European Journal·Jonatan KleimarkPer-Ola Norrby

❮ Previous
Next ❯

Citations

Aug 12, 2015·Organic Letters·Joan R LaoAnton Vidal-Ferran
Jun 3, 2017·Journal of the American Chemical Society·Amy A OttJoseph J Topczewski
May 6, 2015·Organic & Biomolecular Chemistry·K G M Kou, V M Dong
Mar 13, 2019·Organic & Biomolecular Chemistry·Jiawei YangYongzheng Chen
Apr 24, 2021·Journal of the American Chemical Society·Patrick D ParkerVy M Dong
Jan 22, 2015·Journal of the American Chemical Society·Qing-An ChenVy M Dong
Jan 30, 2019·Organic Letters·Chen WuPatrick J Walsh
Aug 11, 2017·Crystal Growth & Design·Anthonius H J EngwerdaElias Vlieg
Jun 18, 2014·Journal of the American Chemical Society·Kevin G M KouVy M Dong
Dec 4, 2019·Organometallics·Ben J TicknerSimon B Duckett
May 26, 2017·Journal of the American Chemical Society·Tiezheng JiaPatrick J Walsh
Nov 23, 2021·The Journal of Organic Chemistry·Kosho MakinoHideyo Takahashi

❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.