An easy and general sequenced elimination/reduction process by means of samarium diiodide, in the presence of D(2)O, provides an efficient method for synthesizing 2,3-dideuterioesters 2. The reaction can be also carried out in the presence of H(2)O instead of D(2)O, yielding the corresponding saturated esters 4. Other deuterated esters have been also obtained. A mechanism to explain this synthesis has been proposed.
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http://dx.doi.org/10.1021/jo026043a | DOI Listing |
J Org Chem
December 2024
Department of Chemistry, Shanghai University, 99 Shangda Road, Shanghai 200444, China.
The first deoxygenative hydrosilylation of ketones promoted by samarium diiodide and samarium has been reported. In this approach, secondary alkyl silanes are synthesized from unactivated ketones and chlorosilanes in one step. The carbonyl group of ketones is activated by SmI-mediated single-electron transfer process, which follows a deoxygenative elimination of O=Sm.
View Article and Find Full Text PDFOrg Biomol Chem
October 2024
Department of Chemistry, Shanghai University, 99 Shangda Road, Shanghai 200444, China.
A direct deoxygenative hydroborylation of ketones with hydroborane ester promoted by a combination of samarium diiodide, samarium and nickel has been developed. In this method, secondary alkyl borate esters are synthesized from unactivated ketones with hydroborane esters in one step. A broad substrate scope and excellent selectivity toward CO cleavage has been demonstrated.
View Article and Find Full Text PDFScience
August 2024
Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA.
Samarium diiodide (SmI) is a privileged, single-electron reductant deployed in diverse synthetic settings. However, generalizable methods for catalytic turnover remain elusive because of the well-known challenge associated with cleaving strong Sm-O bonds. Prior efforts have focused on the use of highly reactive oxophiles to enable catalyst turnover.
View Article and Find Full Text PDFChem Pharm Bull (Tokyo)
April 2024
Graduate School of Pharmaceutical Sciences, The University of Tokyo.
Batrachotoxin (1) is a potent cardio- and neurotoxic steroid isolated from certain species of frogs, birds, and beetles. We previously disclosed two synthetic routes to 1. During our synthetic studies toward 1, we explored an alternative strategy for efficiently assembling its 6/6/6/5-membered steroidal skeleton (ABCD-ring).
View Article and Find Full Text PDFChemistry
May 2024
Institut für Chemie und Biochemie, Freie Universität Berlin, Arnimallee 22, 14195, Berlin, Germany.
This study analyzes the samarium diiodide-promoted cyclizations of 5-arylpentan-2-ones to dearomatized bicyclic products utilizing density functional theory. The reaction involves a single electron transfer to the carbonyl group, which occurs synchronously with the rate determining cyclization event, and a second subsequent proton-coupled electron transfer. These redox reactions are accurately computed employing small core pseudo potentials explicitly involving all f-electrons of samarium.
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