Diastereoselective silylene transfer reactions to chiral enantiopure alkenes

Effects of ligand size and substrate bias

Christina Z. Rotsides, Keith Woerpel

Research output: Contribution to journalArticle

Abstract

Silylenes are useful reactive intermediates for the stereoselective construction of compounds containing carbon-silicon bonds. Despite their synthetic utility, the development of either an enantioselective or diastereoselective metal-catalyzed silylene transfer reaction, in which ligands on the metal catalyst control stereoselectivity, has not been achieved. In this article, we report that the structure of the alkene is the most important for controlling stereoselectivity in these reactions. The stereochemical course of kinetically controlled silacyclopropanation reactions was not affected by the nature or chirality of the ligands on the metal. When silylene transfer reactions were reversible, however, products can be formed with a high degree of diastereoselectivity (90:10 d.r.).

Original languageEnglish (US)
Pages (from-to)8763-8768
Number of pages6
JournalDalton Transactions
Volume46
Issue number27
DOIs
StatePublished - 2017

Fingerprint

Alkenes
Stereoselectivity
Metals
Ligands
Substrates
Chirality
Silicon
Carbon
Catalysts

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Diastereoselective silylene transfer reactions to chiral enantiopure alkenes : Effects of ligand size and substrate bias. / Rotsides, Christina Z.; Woerpel, Keith.

In: Dalton Transactions, Vol. 46, No. 27, 2017, p. 8763-8768.

Research output: Contribution to journalArticle

@article{0d23dc037f3f4542ae50126b98350d01,
title = "Diastereoselective silylene transfer reactions to chiral enantiopure alkenes: Effects of ligand size and substrate bias",
abstract = "Silylenes are useful reactive intermediates for the stereoselective construction of compounds containing carbon-silicon bonds. Despite their synthetic utility, the development of either an enantioselective or diastereoselective metal-catalyzed silylene transfer reaction, in which ligands on the metal catalyst control stereoselectivity, has not been achieved. In this article, we report that the structure of the alkene is the most important for controlling stereoselectivity in these reactions. The stereochemical course of kinetically controlled silacyclopropanation reactions was not affected by the nature or chirality of the ligands on the metal. When silylene transfer reactions were reversible, however, products can be formed with a high degree of diastereoselectivity (90:10 d.r.).",
author = "Rotsides, {Christina Z.} and Keith Woerpel",
year = "2017",
doi = "10.1039/c6dt04612f",
language = "English (US)",
volume = "46",
pages = "8763--8768",
journal = "Dalton Transactions",
issn = "1477-9226",
publisher = "Royal Society of Chemistry",
number = "27",

}

TY - JOUR

T1 - Diastereoselective silylene transfer reactions to chiral enantiopure alkenes

T2 - Effects of ligand size and substrate bias

AU - Rotsides, Christina Z.

AU - Woerpel, Keith

PY - 2017

Y1 - 2017

N2 - Silylenes are useful reactive intermediates for the stereoselective construction of compounds containing carbon-silicon bonds. Despite their synthetic utility, the development of either an enantioselective or diastereoselective metal-catalyzed silylene transfer reaction, in which ligands on the metal catalyst control stereoselectivity, has not been achieved. In this article, we report that the structure of the alkene is the most important for controlling stereoselectivity in these reactions. The stereochemical course of kinetically controlled silacyclopropanation reactions was not affected by the nature or chirality of the ligands on the metal. When silylene transfer reactions were reversible, however, products can be formed with a high degree of diastereoselectivity (90:10 d.r.).

AB - Silylenes are useful reactive intermediates for the stereoselective construction of compounds containing carbon-silicon bonds. Despite their synthetic utility, the development of either an enantioselective or diastereoselective metal-catalyzed silylene transfer reaction, in which ligands on the metal catalyst control stereoselectivity, has not been achieved. In this article, we report that the structure of the alkene is the most important for controlling stereoselectivity in these reactions. The stereochemical course of kinetically controlled silacyclopropanation reactions was not affected by the nature or chirality of the ligands on the metal. When silylene transfer reactions were reversible, however, products can be formed with a high degree of diastereoselectivity (90:10 d.r.).

UR - http://www.scopus.com/inward/record.url?scp=85023750785&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85023750785&partnerID=8YFLogxK

U2 - 10.1039/c6dt04612f

DO - 10.1039/c6dt04612f

M3 - Article

VL - 46

SP - 8763

EP - 8768

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 27

ER -