Article: 1994 Merck Frosst Award Lecture. New strategies for the stereoselective synthesis of natural and unnatural products via organometallic reagents and catalysts

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Title1994 Merck Frosst Award Lecture. New strategies for the stereoselective synthesis of natural and unnatural products via organometallic reagents and catalysts
AuthorsLautens, M1
Ren, Y1
Delanghe, P1
Chiu, P1
Ma, S1
Colucci, J1
KeywordsMethylenecyclopropane
Nickel
Oxabicyclic
Palladium
Stereocontrol
Issue Date1995
PublisherN R C Research Press. The Journal's web site is located at http://pubs.nrc-cnrc.gc.ca/cgi-bin/rp/rp2_desc_e?cjc
CitationCanadian Journal Of Chemistry, 1995, v. 73 n. 8, p. 1251-1257 [How to Cite?]
AbstractSamarium in the presence of diiodomethane selectively cyclopropanates an allenic alcohol to yield a methylenecyclopropane with modest to excellent diastereoselectivity. The effect of substituents at the carbinol carbon and the allenic carbon on the diastereoselectivity was investigated. A palladium catalyst was shown to promote the intramolecular cycloaddition of the methylenecyclopropane with an electron-deficient alkyne to yield a methylenecyclopentane. The reaction was stereospecific with retention of stereochemistry as proven by X-ray diffraction. Nickel catalysts accelerate the hydroalumination of oxabicyclo[3.2.1]alkenes, leading to bicyclic trialkylalanes. Upon treatment with a Lewis acid (diisobutylaluminum chloride), the trialkylalanes fragment to provide cycloheptenols. This reaction, followed by an enantioselective enzyme-catalyzed esterification, was used as a key step in a synthesis of the mevinic acid lactone.
ISSN0008-4042
2011 Impact Factor: 1.242
2011 SCImago Journal Rankings: 0.098
DC Field
Value
dc.contributor.authorLautens, M
dc.contributor.authorRen, Y
dc.contributor.authorDelanghe, P
dc.contributor.authorChiu, P
dc.contributor.authorMa, S
dc.contributor.authorColucci, J
dc.date.accessioned2012-10-08T03:08:10Z
dc.date.available2012-10-08T03:08:10Z
dc.date.issued1995
dc.description.abstractSamarium in the presence of diiodomethane selectively cyclopropanates an allenic alcohol to yield a methylenecyclopropane with modest to excellent diastereoselectivity. The effect of substituents at the carbinol carbon and the allenic carbon on the diastereoselectivity was investigated. A palladium catalyst was shown to promote the intramolecular cycloaddition of the methylenecyclopropane with an electron-deficient alkyne to yield a methylenecyclopentane. The reaction was stereospecific with retention of stereochemistry as proven by X-ray diffraction. Nickel catalysts accelerate the hydroalumination of oxabicyclo[3.2.1]alkenes, leading to bicyclic trialkylalanes. Upon treatment with a Lewis acid (diisobutylaluminum chloride), the trialkylalanes fragment to provide cycloheptenols. This reaction, followed by an enantioselective enzyme-catalyzed esterification, was used as a key step in a synthesis of the mevinic acid lactone.
dc.description.natureLink_to_subscribed_fulltext
dc.identifier.citationCanadian Journal Of Chemistry, 1995, v. 73 n. 8, p. 1251-1257 [How to Cite?]
dc.identifier.epage1257
dc.identifier.issn0008-4042
2011 Impact Factor: 1.242
2011 SCImago Journal Rankings: 0.098
dc.identifier.issue8
dc.identifier.scopuseid_2-s2.0-0028820203
dc.identifier.spage1251
dc.identifier.urihttp://hdl.handle.net/10722/167532
dc.identifier.volume73
dc.languageeng
dc.publisherN R C Research Press. The Journal's web site is located at http://pubs.nrc-cnrc.gc.ca/cgi-bin/rp/rp2_desc_e?cjc
dc.publisher.placeCanada
dc.relation.ispartofCanadian Journal of Chemistry
dc.subjectMethylenecyclopropane
dc.subjectNickel
dc.subjectOxabicyclic
dc.subjectPalladium
dc.subjectStereocontrol
dc.title1994 Merck Frosst Award Lecture. New strategies for the stereoselective synthesis of natural and unnatural products via organometallic reagents and catalysts
dc.typeArticle
Author Affiliations
  1. University of Toronto