Mechanistic Studies on the Organocatalytic α-Chlorination of Aldehydes: The Role and Nature of Off-Cycle Intermediates

Angewandte Chemie
Sebastian PonathMathias Christmann

Abstract

Herein we report the isolation and characterization of aminal intermediates in the organocatalytic α-chlorination of aldehydes. These species are stable covalent ternary adducts of the substrate, the catalyst and the chlorinating reagent. NMR-assisted kinetic studies and isotopic labeling experiments with the isolated intermediate did not support its involvement in downstream stereoselective processes as proposed by Blackmond. By tuning the reactivity of the chlorinating reagent, we were able to suppress the accumulation of rate-limiting off-cycle intermediates. As a result, an efficient and highly enantioselective catalytic system with a broad functional group tolerance was developed.

References

Apr 1, 2004·Journal of the American Chemical Society·Michael P BrochuDavid W C MacMillan
Apr 15, 2004·Journal of the American Chemical Society·Nis HallandKarl Anker Jørgensen
Oct 13, 2005·Chemistry : a European Journal·Nis HallandKarl Anker Jørgensen
Jan 16, 2007·The Journal of Organic Chemistry·Renata Marcia de FigueiredoMathias Christmann
Mar 31, 2007·Science·Teresa D BeesonDavid W C Macmillan
Jan 12, 2008·Angewandte Chemie·Renata Marcia de FigueiredoMathias Christmann
Jul 23, 2009·Chemical Society Reviews·Søren Bertelsen, Karl Anker Jørgensen
Sep 30, 2010·Journal of the American Chemical Society·David C PowersTobias Ritter
Mar 29, 2012·Journal of the American Chemical Society·Jordi BurésDonna G Blackmond
Feb 2, 2013·Organic & Biomolecular Chemistry·Shira D Halperin, Robert Britton
Apr 5, 2013·Organic Letters·Vijay DhandRobert Britton
Apr 24, 2015·Nature Communications·Milan Bergeron-BrlekRobert Britton
Oct 2, 2015·Chemistry : a European Journal·Stanley ChangRobert Britton
Feb 3, 2016·Accounts of Chemical Research·Jordi BurésDonna G Blackmond
Nov 2, 2017·Journal of the American Chemical Society·Tamás FöldesImre Pápai

❮ Previous
Next ❯

Citations

May 1, 2021·Journal of the American Chemical Society·George HutchinsonJordi Burés
Jun 26, 2021·Chemical Science·Venugopal Rao ChallaRobert Britton
Mar 29, 2020·Organic Letters·Sami KortetPetri M Pihko
Oct 9, 2021·Chemistry : a European Journal·Lisa-Marie MohrKarl Anker Jørgensen

❮ 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.