Highly diastereoselective arylation of (S)-mandelic acid enolate: enantioselective synthesis of substituted (R)-3-hydroxy-3-phenyloxindoles and (R)-benzylic acids and synthesis of nitrobenzophenones

The Journal of Organic Chemistry
Santiago BarrosoJosé R Pedro

Abstract

An easy access to substituted (R)-3-hydroxy-3-phenyloxindoles, (R)-benzylic acids, and benzophenones is described. The reaction of the lithium enolate of the (2S,5S)-cis-1,3-dioxolan-4-one derived from optically active (S)-mandelic acid and pivalaldehyde with several o- and p-halonitrobenzenes proceeds readily to give the corresponding arylation products in good yields and diastereoselectivities. The reduction of the nitro group with Zn/HCl/EtOH in the o-nitro arylation products with concomitant intramolecular aminolysis of the dioxolanone moiety leads directly to enantiomerically pure (R)-3-hydroxy-3-phenyloxindoles. On the other hand the basic hydrolysis of the dioxolanone moiety in all the arylation products (ortho and para) leads to enantiomerically pure substituted (R)-benzylic acids. The oxidative decarboxylation of these latter with oxygen as terminal oxidant in the presence of pivalaldehyde and the Co(III)-Me2opba complex as catalyst gives substituted nitrobenzophenones.

References

Jan 5, 1996·Journal of Medicinal Chemistry·H R HowardJ Morrone
Aug 1, 1997·Bioorganic & Medicinal Chemistry·D O KiesewetterW C Eckelman
Jun 11, 1999·The American Journal of Physiology·J HaynesT Stevens
May 18, 2000·The Journal of Organic Chemistry·H VervoortR A Epifanio
Sep 16, 2000·The Journal of Organic Chemistry·M P DenieulT Skrydstrup
Dec 14, 2001·Journal of Medicinal Chemistry·T TokunagaR Nagata
Feb 15, 2002·Bioorganic & Medicinal Chemistry Letters·Albert PalomerDavid Mauleón
May 16, 2002·Natural Product Reports·Satoshi Hibino, Tominari Choshi
Oct 12, 2002·The Journal of Organic Chemistry·Hans-René BjørsvikJosé Angel Vedia Merinero
Mar 18, 2003·Bioorganic & Medicinal Chemistry Letters·Ramdas VidyaRichard H Himes
May 9, 2003·Natural Product Reports·Masanori Somei, Fumio Yamada
Aug 30, 2003·Organic & Biomolecular Chemistry·Ludivine ZouteDominique Cahard

❮ Previous
Next ❯

Citations

Sep 2, 2008·Chemical Communications : Chem Comm·Yi-Xia JiaE Peter Kündig
Apr 6, 2006·Angewandte Chemie·Ryo ShintaniTamio Hayashi
Apr 1, 2009·Chemical Reviews·Hideki Amii, Kenji Uneyama
Jul 12, 2008·The Journal of Organic Chemistry·J Mikael Hillgren, Stephen P Marsden

❮ 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.