Regioselective Ring Opening of Di-isopropylsilylenes Derived from 1,3-Diols with Alkyl Lithium Reagents

The selective alkyl lithium-induced ring opening of 1,3-di-isopropylsilylenes is described. The reaction affords a differentially substituted 1,3-diol bearing a silane that resides at the oxygen in the more sterically demanding position. The reaction can be highly selective with a regiochemical pref...

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Published inOrganic letters Vol. 17; no. 21; pp. 5196 - 5199
Main Authors Chando, Katelyn M, Bailey, Patricia A, Abramite, Joseph A, Sammakia, Tarek
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 06.11.2015
Amer Chemical Soc
Subjects
Alcohols - chemistry
Chemistry
Chemistry, Organic
Indicators and Reagents
Lithium - chemistry
Molecular Structure
Physical Sciences
Science & Technology
Silanes - chemistry
Stereoisomerism
PROTECTING-GROUP
SYSTEM
(+)-PELORUSIDE
COMPOUND
ACETATE ALDOL REACTIONS
INTRAMOLECULAR ALDOL
ENANTIOSELECTIVE TOTAL-SYNTHESIS
PELORUSIDE
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Summary:The selective alkyl lithium-induced ring opening of 1,3-di-isopropylsilylenes is described. The reaction affords a differentially substituted 1,3-diol bearing a silane that resides at the oxygen in the more sterically demanding position. The reaction can be highly selective with a regiochemical preference up to >50:1 and likely proceeds via an alkoxy-silane intermediate. This intermediate can by trapped by methyl iodide to provide the corresponding silyl methyl ether, wherein the silane again resides at the oxygen in the more sterically demanding position.
Bibliography:NIH RePORTER
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ISSN:1523-7060
1523-7052
DOI:10.1021/acs.orglett.5b02529