Sklute Genia, Marek Ilan
Mallat Family Laboratory of Organic Chemistry, Department of Chemistry, Institute of Catalysis Science and Technology and The Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa 32000 Israel.
J Am Chem Soc. 2006 Apr 12;128(14):4642-9. doi: 10.1021/ja060498q.
The combined regio- and stereo-controlled carbometalation reaction of alkynyl sulfoxide followed by a zinc homologation and finally an allylation reaction led, in a single-pot operation, to chiral homoallylic alcohols in excellent yields and diastereoselectivities for the creation of chiral quaternary and tertiary centers. The key features in all of the reactions that are described in this article are the high degree of stereocontrol, the level of predictability, and "the ease of execution" which ensures success in the application of such methods. The chiral sulfinyl moiety can be finally removed by simple treatment with alkyllithiums, which allows further functionalizations of the carbon skeleton. By using one of these methods, the creation of chiral quaternary centers with the smallest possible difference, namely CD3 versus CH3 and 13CH3 versus CH3, was easily performed.
