Stereoselective TiCl4-Promoted Nucleophilic Substitution at C-2 of (4S,5S)-2-Alkyl-4-methyl-5-trifluoromethyl-1,3-dioxolanes

Carlo F. Morelli; Lavinia Durì; Alberto Saladino; Giovanna Speranza; Paolo Manitto

doi:10.1055/s-2004-834884

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Stereoselective TiCl₄-Promoted Nucleophilic Substitution at C-2 of (4S,5S)-2-Alkyl-4-methyl-5-trifluoromethyl-1,3-dioxolanes

Carlo F. Morelli*, Lavinia Durì, Alberto Saladino, Giovanna Speranza, Paolo Manitto
Dipartimento di Chimica Organica e Industriale, Università degli Studi di Milano, via Venezian, 21, 20133 Milano, Italy
Fax: +39(02)50314072; e-Mail: carlo.morelli@unimi.it;

Abstract

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Abstract

TiCl₄-mediated nucleophilic ring-opening reactions of chiral acetals derived from (2S,3S)-1,1,1-trifluorobutane-2,3-diol proceed in a completely regioselective manner, leading to the break of the O1-C2 bond accompanied by a high degree of stereoselectivity. The use of triethylsilyl deuteride or allyltributyltin as nucleophiles gives access, after removal of the chiral auxiliary, to stereoselectively deuterated primary alcohols or homoallylic secondary alcohols, respectively, with high enantiomeric excesses.

Key words

Acetals - ring opening - chiral auxiliary - allylations - stereoselectivity

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References

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