Mechanistic investigations of the palladium-catalyzed aerobic oxidative kinetic resolution of secondary alcohols using (-)-sparteine

Journal of the American Chemical Society
Jaime A Mueller, Matthew S Sigman

Abstract

The mechanistic details of the Pd(II)/(-)-sparteine-catalyzed aerobic oxidative kinetic resolution of secondary alcohols were elucidated, and the origin of asymmetric induction was determined. Saturation kinetics were observed for rate dependence on [(-)-sparteine]. First-order rate dependencies were observed for both the Pd((-)-sparteine)Cl(2) concentration and the alcohol concentration at high and low [(-)-sparteine]. The oxidation rate was inhibited by addition of (-)-sparteine HCl. At low [(-)-sparteine], Pd-alkoxide formation is proposed to be rate limiting, while at high [(-)-sparteine], beta-hydride elimination is proposed to be rate determining. These conclusions are consistent with the measured kinetic isotope effect of k(H)/k(D) = 1.31 +/- 0.04 and a Hammett rho value of -1.41 +/- 0.15 at high [(-)-sparteine]. Calculated activation parameters agree with the change in the rate-limiting step by increasing [(-)-sparteine] with DeltaH(++) = 11.55 +/- 0.65 kcal/mol, DeltaS(++) = -24.5 +/- 2.0 eu at low [(-)-sparteine], and DeltaH(++) = 20.25 +/- 0.89 kcal/mol, DeltaS() = -5.4 +/- 2.7 eu at high [(-)-sparteine]. At high [(-)-sparteine], the selectivity is influenced by both a thermodynamic difference in the stability of the...Continue Reading

References

Apr 21, 2001·The Journal of Organic Chemistry·T NishimuraS Uemura
Jul 27, 2001·Journal of the American Chemical Society·D R JensenM S Sigman
Aug 2, 2001·Journal of the American Chemical Society·E M Ferreira, B M Stoltz
Jul 11, 2002·Journal of the American Chemical Society·Jaime A MuellerMatthew S Sigman
Oct 3, 2002·Journal of the American Chemical Society·Michael J DeardenPeter O'Brien

❮ Previous
Next ❯

Citations

Dec 15, 2005·Journal of the American Chemical Society·Raissa M TrendBrian M Stoltz
Apr 23, 2005·The Journal of Organic Chemistry·Mitchell J SchultzMatthew S Sigman
Aug 8, 2009·Chemical Communications : Chem Comm·Keith M Gligorich, Matthew S Sigman
May 8, 2010·Chemical Communications : Chem Comm·Shigeki MoriHironao Sajiki
Dec 15, 2015·Journal of the American Chemical Society·Yuntao ZhouLei You
Jun 9, 2005·Angewandte Chemie·Edwin Vedejs, Mara Jure
Aug 27, 2005·Biopolymers·Giulia LiciniPaolo Scrimin
Aug 6, 2019·ChemSusChem·Guillermo NicolauCeri Hammond
Apr 29, 2015·Chemistry : a European Journal·Yuntao ZhouEric V Anslyn
Nov 18, 2010·Chemical Communications : Chem Comm·Hong LiXiaobing Wan
Feb 11, 2009·Chemistry : a European Journal·Shuifa QiuGuosheng Liu
Dec 22, 2005·Journal of the American Chemical Society·Bingtao GuanZhangjie Shi
Mar 22, 2006·Accounts of Chemical Research·Matthew S Sigman, David R Jensen
Jul 20, 2013·Journal of the American Chemical Society·Kodai SaitoTakahiko Akiyama
Oct 5, 2017·Chemical Reviews·Dian WangShannon S Stahl
Feb 6, 2013·Organic Letters·Biao JiangZuo-Gang Huang
Jun 14, 2018·Journal of Chemical Information and Modeling·Lorena Simón-VidalHumberto González-Díaz
Jul 27, 2006·Journal of the American Chemical Society·Robert J Nielsen, William A Goddard
Aug 17, 2004·The Journal of Organic Chemistry·Michael J DeardenPeter O'Brien
Oct 20, 2005·Journal of the American Chemical Society·Jaime A MuellerMatthew S Sigman
Sep 13, 2003·The Journal of Organic Chemistry·Sunil K Mandal, Matthew S Sigman
Mar 14, 2007·Inorganic Chemistry·Candace N Cornell, Matthew S Sigman
Feb 25, 2006·The Journal of Organic Chemistry·Bradley A SteinhoffShannon S Stahl
Nov 13, 2004·Journal of the American Chemical Society·Revital CohenMark A Ratner

❮ 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.