Nozaki−Hiyama−Kishi Reactions Catalytic in Chromium

• Published in: Journal of the American Chemical Society 1996-12, Vol.118 (49), p.12349-12357
• Main Authors: Fürstner, Alois, Shi, Nongyuan
• Format: Article
• Language: English
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja9625236

A procedure is described which allows for the first time to perform chromium-catalyzed additions of organic halides to aldehydes (“Nozaki−Hiyama−Kishi reactions”). The reactions are mediated by trimethylchlorosilane, and the active Cr2+ species is constantly recycled by means of nontoxic, commercial manganese powder as the stoichiometric reductant. This method nicely applies to different substituted aryl, heteroaryl, alkynyl, alkenyl, and allyl halides as well as to alkenyl triflates as the starting materials and rivals its stoichiometric precedent in terms of efficiency, practicability, and chemo- and diastereoselectivity. Specifically, it has been demonstrated that the addition of crotyl bromide to various aldehydes is highly stereoconvergent, i.e. the respective anti-configurated homoallyl alcohols are obtained with excellent diastereomeric excess independent of whether the starting halide is (E)- or (Z)-configurated. In accordance with the likely catalytic cycle, both CrCl2(cat.) or CrCl3(cat) turned out to efficiently mediate reactions of this type, with the latter being preferred for practical reasons. Finally, attempts were made to optimize the number of turnovers in chromium. In this context the use of either chromocene (Cp2Cr) or CpCrCl2·THF as “pre-catalysts” were found to significantly upgrade the efficiency of such C−C bond formations, with ≤1 mol % of chromium being required in these cases for quantitative conversions.