Highly enantioselective conjugate addition of nitroalkanes to alkylidenemalonates using efficient phase-transfer catalysis of N-spiro chiral ammonium bromides

Journal of the American Chemical Society
Takashi OoiKeiji Maruoka

Abstract

Highly enantioselective conjugate addition of nitroalkanes to alkylidenemalonates has been accomplished for the first time by the utilization of efficient phase-transfer catalysis of N-spiro C2-symmetric chiral quaternary ammonium bromide 1. For instance, simple mixing of nitropropane (2, R1 = Et), diisopropyl benzylidienemalonate (3, R2 = Ph), Cs2CO3 (1 equiv), and (S,S)-1 (1 mol %) in toluene at 0 degrees C for 2.5 h gave rise to the desired conjugate addition product 4 (R1 = Et, R2 = Ph) quantitatively (anti/syn = 86:14) with 97% ee (anti isomer). The applicability of this procedure has been demonstrated with other representative alkylidenemalonates and nitroalkanes. Since 4 can be readily transformed into the corresponding gamma-amino acid hydrochloride 5 without loss of diastereo- and enantioselectivity, the present method provides a new and practical access to various optically active gamma-amino acid derivatives.

References

Sep 15, 2000·Organic Letters·S Hanessian, V Pham
Nov 30, 2002·Angewandte Chemie·Prasad L Polavarapu

❮ Previous
Next ❯

Citations

Jul 9, 2009·Chemical Communications : Chem Comm·Hai-Hua LuWen-Jing Xiao
Dec 23, 2015·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Iris J Montoya-BalbásPerla Román-Bravo
Jan 3, 2007·Drug Discovery Today·Matthew J GauntNgoc T Vo
Jan 24, 2015·Nature Chemistry·Craig P JohnstonMartin D Smith
Aug 15, 2006·Angewandte Chemie·Jin Young LeeSunggak Kim
May 26, 2007·Angewandte Chemie·Takashi Ooi, Keiji Maruoka
Nov 6, 2009·Angewandte Chemie·Andrea BaschieriMauro F A Adamo
Apr 5, 2007·Chemical Communications : Chem Comm·Keiji MaruokaTaichi Kano
Apr 19, 2012·Chemical Society Reviews·Claudio PalomoJesús M García
Jan 18, 2018·Chemical Communications : Chem Comm·Meiling TanJingsong You
Jan 16, 2019·Proceedings of the Japan Academy. Series B, Physical and Biological Sciences·Keiji Maruoka
Dec 13, 2007·Chemical Reviews·Takuya Hashimoto, Keiji Maruoka
Mar 10, 2005·Chemical Reviews·Roberto BalliniMarino Petrini

❮ Previous
Next ❯

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.