Secondary Allyltitanium(IV) Reagents in Aldehyde Allylation I: Extension of the Hoppe Reaction to γ-Alkoxy Secondary Allyl Carbamates

Patrick Razon; Sylvie Dhulut; Sophie Bezzenine-Lafollée; Jacques Courtieu; Ange Pancrazi; Janick Ardisson

doi:10.1055/s-2004-834912

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Secondary Allyltitanium(IV) Reagents in Aldehyde Allylation I: Extension of the Hoppe Reaction to γ-Alkoxy Secondary Allyl Carbamates

Patrick Razon^a, Sylvie Dhulut^a, Sophie Bezzenine-Lafollée^a, Jacques Courtieu*^a, Ange Pancrazi^b, Janick Ardisson*^b
^a Laboratoire de Chimie Structurale Organique, ICMO, URA CNRS 1384, Université de Paris Sud, 91405 Orsay, France
Fax: +33(1)69158105; e-Mail: courtieu@icmo.u-psud.fr;
^b Laboratoire de Synthèse Organique Sélective et Chimie Organométallique, CNRS-UCP-ESCOM, UMR 8123, ESCOM, Bat E, 13 Bd de l’Hautil, 95092 Cergy-Pontoise, France
Fax: +33(1)307561; e-Mail: janick.ardisson@chim.u-cergy.fr;

Abstract

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Abstract

An efficient access to optically active (R)- or (S)-γ-alkoxy allyltitanium(IV) intermediates, in aldehyde allylation reactions, is described. Enantiomeric γ-alkoxy secondary allyl carbamates (R)- and (S)-14 were first prepared. Determination of their enantiomeric excess was realised on the corresponding deuterated isotopic derivatives by NMR in chiral liquid media. Subsequent aldehyde allylation reaction with propanal performed under Hoppe n-BuLi·(-)-sparteine/Ti(Oi-Pr)₄ or n-BuLi·TMEDA/Ti(Oi-Pr)₄ conditions, led to both enantiomeric homoallylic alcohols 15 or ent-15 in 90% yield, 100% ed and 80% ee.

Key words

Hoppe allylation - allyltitanium reagent - ¹H NMR chiral nematic solvent - Sharpless resolution

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