Synthesis of chiral chromans by the Pd-catalyzed asymmetric allylic alkylation (AAA): scope, mechanism, and applications

Journal of the American Chemical Society
Barry M TrostCatherine Sylvain

Abstract

The Pd-catalyzed asymmetric allylic alkylation (AAA) of phenol allyl carbonates serves as an efficient strategy to construct the allylic C-O bond allowing access to chiral chromans in up to 98% ee. The effect of pH and the influence of olefin geometry, as well as substitution pattern on the ee and the absolute configuration of the chiral chromans were explored in detail. These observations suggest a mechanism involving the cyclization of the more reactive pi-allyl palladium diastereomeric intermediate as the enantiodiscriminating step (Curtin-Hammett conditions). This methodology led to the enantioselective synthesis of the vitamin E core, the first enantioselective total synthesis of (+)-clusifoliol and (-)-siccanin, and the synthesis of an advanced intermediate toward (+)-rhododaurichromanic acid A.

References

Jul 13, 2000·Accounts of Chemical Research·G Helmchen, A Pfaltz
Jul 18, 2001·Journal of the American Chemical Society·C S Campos-FernándezK R Dunbar
Feb 5, 2002·Chemical & Pharmaceutical Bulletin·Barry M Trost
Aug 14, 2003·Chemical Reviews·Barry M Trost, Matthew L Crawley

❮ Previous
Next ❯

Citations

Dec 28, 2012·Journal of the American Chemical Society·Christopher W am EndeKathlyn A Parker
Feb 10, 2012·The Journal of Organic Chemistry·Jeffrey S CannonNicole S Solomon
Sep 9, 2005·Organic Letters·David J Maloney, Sidney M Hecht
Jan 26, 2010·Nature Chemical Biology·Markus LeibelingDaniel B Werz
Jul 19, 2014·Science·Muhammet UyanikKazuaki Ishihara
Jul 19, 2014·Science·Boris J Nachtsheim
Feb 18, 2016·Chemical Reviews·Liang HongRui Wang
Oct 31, 2015·Expert Opinion on Therapeutic Patents·Maria Koufaki
Sep 25, 2015·Journal of the American Chemical Society·Pu-Sheng WangLiu-Zhu Gong
Dec 21, 2016·Organic Letters·Marllon Nascimento de OliveiraJanine Cossy
Mar 4, 2017·The Journal of Organic Chemistry·Scott E Denmark, David J P Kornfilt
Mar 16, 2017·Chemistry : a European Journal·Xiangzhen MengYimin Hu
Nov 4, 2016·Organic & Biomolecular Chemistry·Ryunosuke YoshidaToshiyuki Kan
Sep 11, 2014·Chemistry : a European Journal·Zhongtao WuAdriaan J Minnaard
Sep 27, 2006·Chemistry : a European Journal·Lutz F TietzeKonrad M Sommer
Oct 31, 2007·Angewandte Chemie·Zhan Lu, Shengming Ma
Feb 12, 2008·Organic & Biomolecular Chemistry·Andrey V ZaytsevArthur James
Oct 1, 2005·Chemistry : a European Journal·Barry M TrostJia Xie
Feb 1, 2006·Angewandte Chemie·Christian GrütterWolf-D Woggon
May 8, 2013·Chemistry : a European Journal·Lutz F TietzeSven Heidemann
Nov 10, 2013·Organic & Biomolecular Chemistry·Ryota MiyajiSeijiro Matsubara
May 25, 2021·Organic & Biomolecular Chemistry·So Won Youn, Cheon-Gyu Cho

❮ 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.