Stereospecific Si-C coupling and remote control of axial chirality by enantioselective palladium-catalyzed hydrosilylation of maleimides.

Nature Communications
Xing-Wei GuLi-Wen Xu

Abstract

Hydrosilylation of unsaturated carbon-carbon bonds with hydrosilanes is a very important process to access organosilicon compounds and ranks as one of the most fundamental reactions in organic chemistry. However, catalytic asymmetric hydrosilylation of activated alkenes and internal alkenes has proven elusive, due to competing reduction of carbon-carbon double bond or isomerization processes. Herein, we report a highly enantioselective Si-C coupling by hydrosilylation of carbonyl-activated alkenes using a palladium catalyst with a chiral TADDOL-derived phosphoramidite ligand, which inhibits O-hydrosilylation/olefin reduction. The stereospecific Si-C coupling/hydrosilylation of maleimides affords a series of silyl succinimides with up to 99% yield, >99:1 diastereoselectivity and >99:1 enantioselectivity. The high degree of stereoselectivity exerts remote control of axial chirality, leading to functionalized, axially chiral succinimides which are versatile building blocks. The product utility is highlighted by the enantioselective construction of N-heterocycles bearing up to three stereocenters.

References

Dec 7, 2007·Journal of the American Chemical Society·Valentina DichiaranteAngelo Albini
Jan 30, 2009·Chemistry : a European Journal·Renzo RuzziconiManfred Schlosser
Jul 12, 2011·Chemistry : a European Journal·Meryem BenohoudPetri M Pihko
Aug 17, 2012·Organic Letters·Swapnil Singh, Scott McN Sieburth
Oct 16, 2012·Journal of Medicinal Chemistry·Annaliese K Franz, Sean O Wilson
Jul 10, 2014·Journal of the American Chemical Society·Nicola Di IorioGiorgio Bencivenni
Feb 26, 2015·Chemical Reviews·Chen Cheng, John F Hartwig
Jun 17, 2015·Angewandte Chemie·Zachary D MillerJohn Montgomery
Jun 15, 2016·Chemical Communications : Chem Comm·Ramya RaghunathanJ Sivaguru
Dec 3, 2016·Angewandte Chemie·Aradhana PindwalAaron D Sadow
Jan 25, 2017·Journal of the American Chemical Society·Michael W GribbleStephen L Buchwald
Jun 28, 2017·Journal of the American Chemical Society·Biao ChengZhan Lu
Oct 19, 2017·Journal of Medicinal Chemistry·Remya Ramesh, D Srinivasa Reddy
Dec 30, 2017·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Yavuz Oz, Amitav Sanyal
Jan 11, 2018·Nature Communications·Dakota E McCoyRichard O Prum
Feb 13, 2018·Angewandte Chemie·Zhiguo ZhaoYao Wang
Mar 29, 2018·Journal of the American Chemical Society·Biao ChengZhan Lu
Jun 22, 2018·Nature·Yufan LiangDavid W C MacMillan
Aug 3, 2018·Nature·Ian B PerryDavid W C MacMillan
Aug 11, 2018·Chemistry : a European Journal·João M J M RavascoPedro M P Gois
Dec 17, 2018·Drug Discovery Today. Technologies·Peter A SzijjVijay Chudasama
Dec 10, 2019·Chemical Science·Lucia GarciaMichael S Hill

❮ Previous
Next ❯

Methods Mentioned

BETA
X-ray
column chromatography

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.

Related Papers

Organic Letters
Nicolas SabouraultCharles Mioskowski
Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry
Duo WeiJean-Baptiste Sortais
Chemistry : a European Journal
Dianjun ChenJürgen Klankermayer
Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]
Yumiko NakajimaShigeru Shimada
© 2022 Meta ULC. All rights reserved