Diastereoreactivity of a chiral oxathiane derived from 5-hydroxy-1-tetralone

Arlette Solladié-Cavallo, Milan Balaz, Marta Salisova

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

The diastereoreactivity at the CH2 bridge of a cis-oxathiane derived from 5-hydroxy-1-tetralone (unprotected and protected at the OH) was studied, and it appeared that all reactions at C-2 provided equatorial substitution. It was also found that: i) reductions of the equatorial benzoyl derivative with selectrides provided high diastereoselectivities at C-2' while LAH did not. Methyl Grignard addition was less selective and the selectivity of the propanoyl analogue was smaller; ii) condensation of aldehydes and/or ketones with the lithio derivative provided high equatorial diastereoselectivities at C-2 but low of nil diastereoselectivities at C-2′; iii) lithiation at C-2 was possible only with the oxathiane unsubstituted at C-2 (CH2) and not possible with derivatives substituted at C-2 (CHR), perhaps due to the conformational rigidity of this oxathiane in the lithiation transition state and to the equatorial demand of all substituents at C-2, including lithium.

Original languageEnglish
Pages (from-to)337-345
Number of pages9
JournalEuropean Journal of Organic Chemistry
Issue number2
DOIs
Publication statusPublished - 2003 Jan 1

Fingerprint

aldehydes
rigidity
ketones
condensation
lithium
selectivity
substitutes
analogs
Derivatives
Ketones
Lithium
Aldehydes
Rigidity
Condensation
Substitution reactions
5-hydroxy-1-tetralone
oxathiane

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cite this

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title = "Diastereoreactivity of a chiral oxathiane derived from 5-hydroxy-1-tetralone",
abstract = "The diastereoreactivity at the CH2 bridge of a cis-oxathiane derived from 5-hydroxy-1-tetralone (unprotected and protected at the OH) was studied, and it appeared that all reactions at C-2 provided equatorial substitution. It was also found that: i) reductions of the equatorial benzoyl derivative with selectrides provided high diastereoselectivities at C-2' while LAH did not. Methyl Grignard addition was less selective and the selectivity of the propanoyl analogue was smaller; ii) condensation of aldehydes and/or ketones with the lithio derivative provided high equatorial diastereoselectivities at C-2 but low of nil diastereoselectivities at C-2′; iii) lithiation at C-2 was possible only with the oxathiane unsubstituted at C-2 (CH2) and not possible with derivatives substituted at C-2 (CHR), perhaps due to the conformational rigidity of this oxathiane in the lithiation transition state and to the equatorial demand of all substituents at C-2, including lithium.",
author = "Arlette Solladi{\'e}-Cavallo and Milan Balaz and Marta Salisova",
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Diastereoreactivity of a chiral oxathiane derived from 5-hydroxy-1-tetralone. / Solladié-Cavallo, Arlette; Balaz, Milan; Salisova, Marta.

In: European Journal of Organic Chemistry, No. 2, 01.01.2003, p. 337-345.

Research output: Contribution to journalArticle

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N2 - The diastereoreactivity at the CH2 bridge of a cis-oxathiane derived from 5-hydroxy-1-tetralone (unprotected and protected at the OH) was studied, and it appeared that all reactions at C-2 provided equatorial substitution. It was also found that: i) reductions of the equatorial benzoyl derivative with selectrides provided high diastereoselectivities at C-2' while LAH did not. Methyl Grignard addition was less selective and the selectivity of the propanoyl analogue was smaller; ii) condensation of aldehydes and/or ketones with the lithio derivative provided high equatorial diastereoselectivities at C-2 but low of nil diastereoselectivities at C-2′; iii) lithiation at C-2 was possible only with the oxathiane unsubstituted at C-2 (CH2) and not possible with derivatives substituted at C-2 (CHR), perhaps due to the conformational rigidity of this oxathiane in the lithiation transition state and to the equatorial demand of all substituents at C-2, including lithium.

AB - The diastereoreactivity at the CH2 bridge of a cis-oxathiane derived from 5-hydroxy-1-tetralone (unprotected and protected at the OH) was studied, and it appeared that all reactions at C-2 provided equatorial substitution. It was also found that: i) reductions of the equatorial benzoyl derivative with selectrides provided high diastereoselectivities at C-2' while LAH did not. Methyl Grignard addition was less selective and the selectivity of the propanoyl analogue was smaller; ii) condensation of aldehydes and/or ketones with the lithio derivative provided high equatorial diastereoselectivities at C-2 but low of nil diastereoselectivities at C-2′; iii) lithiation at C-2 was possible only with the oxathiane unsubstituted at C-2 (CH2) and not possible with derivatives substituted at C-2 (CHR), perhaps due to the conformational rigidity of this oxathiane in the lithiation transition state and to the equatorial demand of all substituents at C-2, including lithium.

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