Homochiral ketals in organic synthesis. Diastereoselective cyclopropanation of α,β-unsaturated ketals derived from 1,4-D1-O-benzyl-l-threitol

Eugene A Mash, Keith A. Nelson

Research output: Contribution to journalArticle

75 Citations (Scopus)

Abstract

2-Cycloalken-1-one 1,4-di -O-benzyl -L-threitol ketals undergo efficient and diastereoselective cyclopropanation when treated with an excess of the Simmons-Smith reagent. For example, 2-cyclohexen-1-one 1,4-di -O-benzyl -L-threitol ketal gave in 90-98% yield a 9:1 mixture of diastereomeric cyclopropanes as established by 62.9 MHz 13C NMR spectroscopy and by hydrolysis of the mixture to (1R,6S)-bicyclo[4.1.0] heptan-2-one. Sixteen other examples are presented which demonstrate the generality and predictability of the process for 2-cycloalken-1-one ketals, as wall as an unfortunate lack of diastereoselectivity for α,β-unsaturated 1,4-di-O-benzyl-L-threitol acetals.

Original languageEnglish (US)
Pages (from-to)679-692
Number of pages14
JournalTetrahedron
Volume43
Issue number4
DOIs
StatePublished - 1987

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Synthetic Chemistry Techniques
Cyclopropanes
Acetals
Nuclear magnetic resonance spectroscopy
Hydrolysis
Magnetic Resonance Spectroscopy
threitol

ASJC Scopus subject areas

  • Biochemistry
  • Organic Chemistry
  • Drug Discovery

Cite this

Homochiral ketals in organic synthesis. Diastereoselective cyclopropanation of α,β-unsaturated ketals derived from 1,4-D1-O-benzyl-l-threitol. / Mash, Eugene A; Nelson, Keith A.

In: Tetrahedron, Vol. 43, No. 4, 1987, p. 679-692.

Research output: Contribution to journalArticle

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abstract = "2-Cycloalken-1-one 1,4-di -O-benzyl -L-threitol ketals undergo efficient and diastereoselective cyclopropanation when treated with an excess of the Simmons-Smith reagent. For example, 2-cyclohexen-1-one 1,4-di -O-benzyl -L-threitol ketal gave in 90-98{\%} yield a 9:1 mixture of diastereomeric cyclopropanes as established by 62.9 MHz 13C NMR spectroscopy and by hydrolysis of the mixture to (1R,6S)-bicyclo[4.1.0] heptan-2-one. Sixteen other examples are presented which demonstrate the generality and predictability of the process for 2-cycloalken-1-one ketals, as wall as an unfortunate lack of diastereoselectivity for α,β-unsaturated 1,4-di-O-benzyl-L-threitol acetals.",
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N2 - 2-Cycloalken-1-one 1,4-di -O-benzyl -L-threitol ketals undergo efficient and diastereoselective cyclopropanation when treated with an excess of the Simmons-Smith reagent. For example, 2-cyclohexen-1-one 1,4-di -O-benzyl -L-threitol ketal gave in 90-98% yield a 9:1 mixture of diastereomeric cyclopropanes as established by 62.9 MHz 13C NMR spectroscopy and by hydrolysis of the mixture to (1R,6S)-bicyclo[4.1.0] heptan-2-one. Sixteen other examples are presented which demonstrate the generality and predictability of the process for 2-cycloalken-1-one ketals, as wall as an unfortunate lack of diastereoselectivity for α,β-unsaturated 1,4-di-O-benzyl-L-threitol acetals.

AB - 2-Cycloalken-1-one 1,4-di -O-benzyl -L-threitol ketals undergo efficient and diastereoselective cyclopropanation when treated with an excess of the Simmons-Smith reagent. For example, 2-cyclohexen-1-one 1,4-di -O-benzyl -L-threitol ketal gave in 90-98% yield a 9:1 mixture of diastereomeric cyclopropanes as established by 62.9 MHz 13C NMR spectroscopy and by hydrolysis of the mixture to (1R,6S)-bicyclo[4.1.0] heptan-2-one. Sixteen other examples are presented which demonstrate the generality and predictability of the process for 2-cycloalken-1-one ketals, as wall as an unfortunate lack of diastereoselectivity for α,β-unsaturated 1,4-di-O-benzyl-L-threitol acetals.

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