An efficient and convenient palladium-catalyzed direct intermolecular silylation of C(sp)-H bonds by using disilanes as the silicon source with the assistance of a readily removable bidentate directing group is reported. This strategy provided a regio- and stereoselective protocol for exclusive synthesis of Z-vinylsilanes with reasonable to excellent yields and good functional group compatibility. Silylation of the isolated palladacycle intermediate revealed the Z-stereoselective pathway. Moreover, the practicality and effectiveness of this method were illustrated by a gram-scale experiment and further functionalization of the silylation product.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.orglett.7b02486 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Stereoselective Synthesis of Z-Vinylsilanes via Palladium-Catalyzed Direct Intermolecular Silylation of C(sp)-H Bonds.
Org Lett
October 2017
School of Chemistry and Chemical Engineering, ‡Key Laboratory for Thin Film and Microfabrication of Ministry of Education, and §Zhiyuan College, Shanghai Jiao Tong University, Shanghai 200240, People's Republic of China.
An efficient and convenient palladium-catalyzed direct intermolecular silylation of C(sp)-H bonds by using disilanes as the silicon source with the assistance of a readily removable bidentate directing group is reported. This strategy provided a regio- and stereoselective protocol for exclusive synthesis of Z-vinylsilanes with reasonable to excellent yields and good functional group compatibility. Silylation of the isolated palladacycle intermediate revealed the Z-stereoselective pathway.
View Article and Find Full Text PDF[1,5]-Brook rearrangement: an overlooked but valuable silyl migration to synthesize configurationally defined vinylsilane. The unique steric and electronic effects of geminal bis(silane).
Chem Commun (Camb)
October 2013
Key Laboratory of Drug-Targeting and Drug Delivery System of the Education Ministry, Department of Medicinal Chemistry, West China School of Pharmacy, Sichuan University, Chengdu, 610041, China.
An unusual [1,5]-Brook rearrangement of the lithium alkoxide of geminal bis(silyl) homoallylic alcohol is described. The unique steric and electronic effects of geminal bis(silane) were found to be crucial for promoting this long-range silyl migration, as well as for facilitating the subsequent γ/Z-selective addition of silyl allyllithium with carbonyl compounds to synthesize diverse configurationally defined Z-vinylsilanes.
View Article and Find Full Text PDFA second-generation total synthesis of (+)-phorboxazole A.
J Org Chem
February 2008
Department of Chemistry, The Penn Center for Molecular Discovery, and Monell Chemical Senses Center, University of Pennsylvania, Philadelphia, Pennsylvania 19104, USA.
A highly convergent second-generation synthesis of (+)-phorboxazole A has been achieved. Highlights of the synthetic approach include improved Petasis-Ferrier union/rearrangement conditions on a scale to assemble multigram quantities of the C(11-15) and C(22-26) cis-tetrahydropyrans inscribed with the phorboxazole architecture, a convenient method to prepare E- and Z-vinyl bromides from TMS-protected alkynes utilizing radical isomerization of Z-vinylsilanes, and a convergent late-stage Stille union to couple a fully elaborated C(1-28) macrocyclic iodide with a C(29-46) oxazole stannane side chain to establish the complete phorboxazole skeleton. The synthesis, achieved with a longest linear sequence of 24 steps, proceeded in 4.
View Article and Find Full Text PDFSynthesis of (Z)-vinylsilanes with high diastereoselectivity by using samarium diiodide.
Org Lett
March 2001
Departamento de Química Orgánica e Inorgánica, Facultad de Química Universidad de Oviedo, Julián Clavería, 8, 33071 Oviedo, Spain.
beta-Elimination of O-acetyl 1-chloro-1-trimethylsilylalkan-2-ols 1 was achieved by using samarium diiodide as a metaling reagent and afforded the corresponding (Z)-vinylsilanes with high stereoselectivity. The starting compounds 1 were easily prepared by treatment of different aldehydes with (chlorolithiomethyl)trimethylsilane and further acetylation.
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!