Exploiting phosphonate chemistry in metal-mediated dearomatization: stereoselective construction of functionalized spirolactams from arene ruthenium complexes

Journal of the American Chemical Society
F Christopher PiggeRashmi Dalvi

Abstract

Arene ruthenium complexes possessing beta-amido phosphonate side chains participate in intramolecular spirocyclization reactions to deliver stable cyclohexadienyl ruthenium adducts. Spirocyclization is accomplished via a tandem two-step sequence that involves stereoselective nucleophilic aromatic addition to the ipso position of the coordinated arene, followed by intermolecular Horner-Wadsworth-Emmons olefination. The resulting eta5-cyclohexadienyl complexes can then be diastereoselectively converted to metal-free azaspiro[4.5]decane derivatives upon oxidative demetalation in the presence of suitable nucleophiles. An asymmetric spirocyclization was demonstrated through application of this procedure to a beta-amido phosphonate prepared from (S)-(-)-alpha-methyl benzylamine. The expected spirolactam product was obtained as a single enantiomer.

References

Dec 26, 2001·Chemical Reviews·A R PapeE P Kündig
Nov 30, 2002·Angewandte Chemie·E Peter KündigGérald Bernardinelli
May 8, 2003·Journal of the American Chemical Society·E Peter KündigSylvie Tchertchian
Feb 14, 2004·The Journal of Organic Chemistry·F Christopher PiggeNigam P Rath

❮ Previous
Next ❯

Citations

Aug 19, 2007·Chemical Communications : Chem Comm·Tannya R Ibarra-RiveraLuis D Miranda
Aug 4, 2018·Chemical Society Reviews·William C WertjesDavid Sarlah
Mar 14, 2007·Angewandte Chemie·F Christopher PiggeErik R Hoefgen
Jul 8, 2009·Angewandte Chemie·Tienan JinYoshinori Yamamoto
Apr 21, 2011·Angewandte Chemie·Stéphane P Roche, John A Porco
Sep 16, 2020·Chemical Communications : Chem Comm·Akshay M NairChandra M R Volla
Nov 20, 2020·Chemistry : a European Journal·Luke J WilliamsJames W Walton
Aug 14, 2008·The Journal of Organic Chemistry·Hiroki IwasakiTetsuaki Tanaka
Sep 9, 2010·Langmuir : the ACS Journal of Surfaces and Colloids·Aruna VelamakanniJaycoda S Major
Sep 28, 2006·Journal of the American Chemical Society·Alireza Ariafard, Zhenyang Lin

❮ 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.