AI Article Synopsis
Article Abstract
Reactions of alpha-sulfinyl carbanions, derived from p-tolyl sulfoxides bearing various alkyl groups, with various electrophiles were examined. The reaction of alpha-sulfinyl carbanions, derived from the beta-silylethyl sulfoxides, with ketones or trimethyl phosphate, gave the syn products with high stereoselectivity. Interaction between the silicon in the trialkylsilyl group and the carbonyl oxygen in nucleophiles was postulated to stabilize the transition state, leading preferably to the syn diastereisomers. This novel silicon-oxygen interaction was supported by an MO calculation study using the MOPAC 93/PM3 and the Gaussian 94 Beche3LYP/3-21+G methods.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/jo9913560 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Synthesis of β-sulfinyl cyclobutane carboxylic amides via a formal α to β sulphoxide migration process.
Org Biomol Chem
June 2019
Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, Complesso Universitario di Monserrato, S.S. 554, Bivio per Sestu, I-09042, Monserrato, Cagliari, Italy.
An original tandem reaction consisting of a thermal elimination-addition process was developed. Highly substituted β-sulfinyl cyclobutane carboxylic acid derivatives were obtained from isomeric α-sulfinyl derivatives in a single operation in good to high yields and with high trans diastereoselectivity.
View Article and Find Full Text PDFα-Sulfinyl Benzoates as Precursors to Li and Mg Carbenoids for the Stereoselective Iterative Homologation of Boronic Esters.
J Am Chem Soc
August 2017
School of Chemistry, University of Bristol, Cantock's Close, BS8 1TS, United Kingdom.
The stereoselective reagent-controlled homologation of boronic esters is one of a small number of iteratable synthetic transformations that if automated could form the basis of a veritable molecule-making machine. Recently, α-stannyl triisopropylbenzoates and α-sulfinyl chlorides have emerged as useful building blocks for the iterative homologation of boronic esters. However, α-stannyl benzoates need to be prepared using stoichiometric amounts of the (+)- or (-)-enantiomer of the scarcely available and expensive diamine sparteine; also, these building blocks, together with the byproducts that are generated during homologation, are perceived as being toxic.
View Article and Find Full Text PDFAlkynyl sulfoxides as α-sulfinyl carbene equivalents: gold-catalysed oxidative cyclopropanation.
Chem Commun (Camb)
May 2017
School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT, UK.
Alkynyl sulfoxides are shown to act as α-sulfinyl metallocarbene synthons under oxidative gold catalysis, enabling reactions that are not available from diazo-precursors. This strategy is exemplified in the synthesis of fused α-sulfinyl cyclopropanes.
View Article and Find Full Text PDFOrganometallic Complex Formed by an Unconventional Radical S-Adenosylmethionine Enzyme.
J Am Chem Soc
August 2016
Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, United States.
Pyrococcus horikoshii Dph2 (PhDph2) is an unusual radical S-adenosylmethionine (SAM) enzyme involved in the first step of diphthamide biosynthesis. It catalyzes the reaction by cleaving SAM to generate a 3-amino-3-carboxypropyl (ACP) radical. To probe the reaction mechanism, we synthesized a SAM analogue (SAMCA), in which the ACP group of SAM is replaced with a 3-carboxyallyl group.
View Article and Find Full Text PDFA new multicomponent reaction: unexpected formation of derivatizable cyclic α-alkoxy isothioureas.
Org Biomol Chem
March 2015
Institut für Chemie, Carl von Ossietzky Universität Oldenburg, P. O. Box 2503, Carl-von-Ossietzky-Str. 9-11, 26111 Oldenburg, Germany.
An unexpected formation of cyclic α-alkoxy isothioureas has been achieved. As is known, the heterocyclic imines 2,5-dihydro-1,3-thiazoles are convertible to bisamides with the aid of a carboxylic acid and an isocyanide (Ugi reaction). Herein, it is shown that 2,5-dihydro-1,3-thiazole S-monoxides-the respective α-sulfinyl imines-are characterized by an altered reaction behavior.
View Article and Find Full Text PDFWant 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!