The unusual reactivity of 9-oxa-4-thia-tetracyclo[5.5.1.02,7.010,13] tridecan-12-one-3-spiro-1 '-cyclopentan-3'-ones: a molecular modelling study | Health & Environmental Research Online (HERO)

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HERO ID

5474109

Reference Type

Journal Article

Title

The unusual reactivity of 9-oxa-4-thia-tetracyclo[5.5.1.02,7.010,13] tridecan-12-one-3-spiro-1 '-cyclopentan-3'-ones: a molecular modelling study

Author(s)

Ferrari, M; Orsini, F; Resmini, M; Sisti, M

Year

1994

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Journal

Journal of Molecular Structure: Theochem
ISSN: 0166-1280
EISSN: 1872-7999

Volume

309

Issue

Page Numbers

105-112

URL

http://www.sciencedirect.com/science/article/pii/0166128094800677
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Abstract

9-Oxa-4-thia-tetracyclo[5.5.1.02,7.010,13]tridecan-12-one-3-spiro-l'-cyclopentan-3'-ones, which are useful intermediates in the total synthesis of sesterterpenes, display an unusual reactivity towards organometallic reagents in that the tetrahydrofuran ring opening precedes the nucleophilic attack on the carbonyl group in the trans diastereoisomer 5. These experimental results, which are of considerable importance from a synthetic point of view, were rationalized using molecular modelling techniques implemented using the AMPAC package. The different behaviour of the cis and trans diastereoisomers is related to the steric strain of the tetrahydrofuran moiety in the latter compound.