Abstract
2-Methyl- and 2-phenyl-substituted oxathianes derived from Myrtenal have been synthesized in satisfying yields. Lithiation of 2-methyl-substituted oxathiane could not be done, but lithiation of 2-phenyl-substituted and non-substituted oxathianes could be performed with s-BuLi. Quenching with D 2O, TMSCI, and/or a carbonyl compound always provides the equatorial product in consistency with a prefered equatorial orientation of the lithium in the lithiated derivatives. A model is proposed to rationalize the diastereoselectivities observed at C5′ during reaction of aldehydes with lithiated non-substituted oxathiane. The model is based on the hypothesis that the lithium, being linked simultaneously to the carbon and the oxygen, is shifted toward the oxygen side, making the steric hindrance of this side more effective. Dimeric side products were observed during formation of these oxathianes (condensation of various aldehydes with the corresponding hydroxythiol), which had not been reported for other oxathianes (derived from pulegone and/or camphorsulfonic acid).
| Original language | English |
|---|---|
| Pages (from-to) | 6619-6626 |
| Number of pages | 8 |
| Journal | Journal of Organic Chemistry |
| Volume | 68 |
| Issue number | 17 |
| DOIs | |
| Publication status | Published - 2003 Sep 1 |
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All Science Journal Classification (ASJC) codes
- Organic Chemistry
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New 1,3-oxathianes derived from Myrtenal : Synthesis and reactivity. / Solladié-Cavallo, Arlette; Balaz, Milan; Salisova, Marta; Welter, Richard.
In: Journal of Organic Chemistry, Vol. 68, No. 17, 01.09.2003, p. 6619-6626.Research output: Contribution to journal › Article
TY - JOUR
T1 - New 1,3-oxathianes derived from Myrtenal
T2 - Synthesis and reactivity
AU - Solladié-Cavallo, Arlette
AU - Balaz, Milan
AU - Salisova, Marta
AU - Welter, Richard
PY - 2003/9/1
Y1 - 2003/9/1
N2 - 2-Methyl- and 2-phenyl-substituted oxathianes derived from Myrtenal have been synthesized in satisfying yields. Lithiation of 2-methyl-substituted oxathiane could not be done, but lithiation of 2-phenyl-substituted and non-substituted oxathianes could be performed with s-BuLi. Quenching with D 2O, TMSCI, and/or a carbonyl compound always provides the equatorial product in consistency with a prefered equatorial orientation of the lithium in the lithiated derivatives. A model is proposed to rationalize the diastereoselectivities observed at C5′ during reaction of aldehydes with lithiated non-substituted oxathiane. The model is based on the hypothesis that the lithium, being linked simultaneously to the carbon and the oxygen, is shifted toward the oxygen side, making the steric hindrance of this side more effective. Dimeric side products were observed during formation of these oxathianes (condensation of various aldehydes with the corresponding hydroxythiol), which had not been reported for other oxathianes (derived from pulegone and/or camphorsulfonic acid).
AB - 2-Methyl- and 2-phenyl-substituted oxathianes derived from Myrtenal have been synthesized in satisfying yields. Lithiation of 2-methyl-substituted oxathiane could not be done, but lithiation of 2-phenyl-substituted and non-substituted oxathianes could be performed with s-BuLi. Quenching with D 2O, TMSCI, and/or a carbonyl compound always provides the equatorial product in consistency with a prefered equatorial orientation of the lithium in the lithiated derivatives. A model is proposed to rationalize the diastereoselectivities observed at C5′ during reaction of aldehydes with lithiated non-substituted oxathiane. The model is based on the hypothesis that the lithium, being linked simultaneously to the carbon and the oxygen, is shifted toward the oxygen side, making the steric hindrance of this side more effective. Dimeric side products were observed during formation of these oxathianes (condensation of various aldehydes with the corresponding hydroxythiol), which had not been reported for other oxathianes (derived from pulegone and/or camphorsulfonic acid).
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U2 - 10.1021/jo034404w
DO - 10.1021/jo034404w
M3 - Article
C2 - 12919025
AN - SCOPUS:0042510068
VL - 68
SP - 6619
EP - 6626
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 17
ER -