Transformation of alpha,beta-epoxyesters into 2,3-dideuterioesters promoted by samarium diiodide.

J Org Chem

Departamento de Química Orgánica e Inorgánica, Facultad de Química, Universidad de Oviedo, Julián Clavería, 8, 33071 Oviedo, Spain.

Published: February 2003

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.

Download full-text PDF

Source
http://dx.doi.org/10.1021/jo026043aDOI Listing

Publication Analysis

Top Keywords

samarium diiodide
8
transformation alphabeta-epoxyesters
4
alphabeta-epoxyesters 23-dideuterioesters
4
23-dideuterioesters promoted
4
promoted samarium
4
diiodide easy
4
easy general
4
general sequenced
4
sequenced elimination/reduction
4
elimination/reduction process
4

Similar Publications

Samarium Diiodide/Samarium-Mediated Deoxygenative Hydrosilylation of Ketones.

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 PDF

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 CO cleavage has been demonstrated.

View Article and Find Full Text PDF

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 PDF

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 PDF

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.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!