Stereoselective Functionalization of Racemic Cyclopropylzinc Reagents via Enantiodivergent Relay Coupling

Journal of the American Chemical Society
Lun AnXingang Zhang

Abstract

Efficient construction of optically pure molecules from readily available starting materials in a simple manner is an ongoing goal in asymmetric synthesis. As a straightforward route, transition-metal-catalyzed enantioconvergent coupling between widely available secondary alkyl electrophiles and organometallic nucleophiles has emerged as a powerful strategy to construct chiral center(s). However, the scope of racemic secondary alkylmetallic nucleophiles for this coupling remains limited in specific substrates because of the difficulties in stereoselective formation of the key alkylmetal intermediates. Here, we report an enantiodivergent strategy to efficiently achieve an array of synthetically useful chiral cyclopropanes, including chiral fluoroalkylated cyclopropanes and enantiomerically enriched cyclopropanes with chiral side chains, from racemic cyclopropylzinc reagents. This strategy relies on a one-pot, two-step enantiodivergent relay coupling process of the racemic cis-cyclopropylzinc reagents with two different electrophiles, which involves kinetic resolution of racemic cis-cyclopropylzinc reagents through a nickel-catalyzed enantioselective coupling with alkyl electrophiles, followed by a stereospecific relay coupling o...Continue Reading

References

Dec 20, 2002·Angewandte Chemie·Viet Anh VuPaul Knochel
Apr 10, 2003·Chemical Reviews·Hélène LebelAndré B Charette
Nov 6, 2004·The Journal of Organic Chemistry·Gary A MolanderPatrick J Carroll
Mar 31, 2005·Journal of the American Chemical Society·Christian Fischer, Gregory C Fu
Mar 16, 2006·Journal of the American Chemical Society·Kevin R CamposCheng-yi Chen
Oct 20, 2007·Clinical Cancer Research : an Official Journal of the American Association for Cancer Research·Karen LibyMichael B Sporn
Jun 24, 2008·Journal of Medicinal Chemistry·William K Hagmann
Mar 31, 2010·Chemical Society Reviews·John C Jewett, Carolyn R Bertozzi
Jun 19, 2010·The Journal of Organic Chemistry·Trisha A DuffeyEdwin Vedejs
May 18, 2012·Chemical Society Reviews·David Y-K ChenJean-Alexandre Richard
Sep 27, 2012·Chemistry : a European Journal·Louis-Philippe B BeaulieuAndré B Charette
Oct 29, 2013·Chemical Society Reviews·Dominique Cahard, Vincent Bizet
Apr 1, 2014·Journal of the American Chemical Society·Yufan Liang, Gregory C Fu
May 16, 2014·Nature·Sarah Z TaskerTimothy F Jamison
Jun 21, 2014·Nature Chemistry·Amadeu BonetVarinder K Aggarwal
Jul 8, 2016·Journal of the American Chemical Society·Marcin OdachowskiVarinder K Aggarwal
Sep 2, 2016·Topics in Current Chemistry·Takanori Iwasaki, Nobuaki Kambe
Oct 25, 2017·Beilstein Journal of Organic Chemistry·Layal HarissAli Hachem
Nov 18, 2017·Journal of the American Chemical Society·Jason P G Rygus, Cathleen M Crudden
Feb 6, 2018·Journal of Medicinal Chemistry·Nicholas A Meanwell
Nov 2, 1998·Angewandte Chemie·Shao-Man ZhouMing-Hua Tang
Jun 2, 2018·Bioorganic & Medicinal Chemistry·Jie ZhuHao-Peng Sun

❮ 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.