New 1,3-oxathianes derived from Myrtenal: Synthesis and reactivity

Arlette Solladié-Cavallo, Milan Balaz, Marta Salisova, Richard Welter

Research output: Contribution to journalArticle

10 Citations (Scopus)

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 languageEnglish
Pages (from-to)6619-6626
Number of pages8
JournalJournal of Organic Chemistry
Volume68
Issue number17
DOIs
Publication statusPublished - 2003 Sep 1

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Lithium
Aldehydes
Oxygen
Carbonyl compounds
myrtenal
oxathiane
Condensation
Quenching
Carbon
Derivatives
Acids
pulegone

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

Cite this

Solladié-Cavallo, Arlette ; Balaz, Milan ; Salisova, Marta ; Welter, Richard. / New 1,3-oxathianes derived from Myrtenal : Synthesis and reactivity. In: Journal of Organic Chemistry. 2003 ; Vol. 68, No. 17. pp. 6619-6626.
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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 journalArticle

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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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