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 language | English |
|---|---|
| Pages (from-to) | 337-345 |
| Number of pages | 9 |
| Journal | European Journal of Organic Chemistry |
| Issue number | 2 |
| DOIs | |
| Publication status | Published - 2003 Jan 1 |
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All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Organic Chemistry
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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 journal › Article
TY - JOUR
T1 - Diastereoreactivity of a chiral oxathiane derived from 5-hydroxy-1-tetralone
AU - Solladié-Cavallo, Arlette
AU - Balaz, Milan
AU - Salisova, Marta
PY - 2003/1/1
Y1 - 2003/1/1
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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UR - http://www.scopus.com/inward/citedby.url?scp=0037245010&partnerID=8YFLogxK
U2 - 10.1002/ejoc.200390039
DO - 10.1002/ejoc.200390039
M3 - Article
AN - SCOPUS:0037245010
SP - 337
EP - 345
JO - Annalen der Pharmacie
JF - Annalen der Pharmacie
SN - 0075-4617
IS - 2
ER -