Diastereomerically pure 1,2-diols by nucleophilic displacement reactions of 3-oxetanols - A study directed towards the identification of suitable nucleophiles and the elucidation of possible side reactions

Thorsten Bach, Frank Eilers

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12 Scopus citations

Abstract

The ring opening of 3-isopropyl-2-phenyl-3-oxetanol (2a) by various nucleophiles has been studied. In the presence of BF3 as a Lewis acid, a clean reaction at the less substituted C-4 position was observed and the corresponding 1,2-diols 6-11 and 21-23 were isolated in diastereomerically pure form (47-97% yield). Alkyl-, aryl-, alkynyl- and alkenyllithium compounds proved to be suitable carbon nucleophiles. Deprotonated thiols were used as sulfur nucleophiles. An alkoxide derived from benzyl alcohol and an amide derived from benzylamine reacted less readily under these conditions, yielding the 1,2,3-trifunctional compounds 24 (42% yield) and 26 (54% yield). Other 2-phenyl-3-oxetanols such as 2b and 2c can also be employed as electrophiles, whereas 2-anisyl derivatives preferentially undergo rearrangement reactions, as exemplified by the conversion of oxetane 16 to the hydroxy ketone 17 (84% yield). The superior behaviour of 3-oxetanols as compared to their silyl derivatives in reactions with nucleophiles became evident from the reaction of 3-silyloxyoxetane 1a with alkyllithium reagents. A β elimination occurred upon treatment with nBuLi, which, after pericyclic ring opening and addition of nBuLi, yielded the allylic alcohol 20.

Original languageEnglish
Pages (from-to)2161-2169
Number of pages9
JournalEuropean Journal of Organic Chemistry
Issue number10
DOIs
StatePublished - Oct 1998
Externally publishedYes

Keywords

  • 1,2-Diols
  • Alkyldealkoxylation
  • Oxetanes
  • Photocycloaddition
  • Ring opening

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