Direct Coupling Reaction between Alcohols and Silyl Compounds:  Enhancement of Lewis Acidity of Me3SiBr Using InCl3

• Published in: Journal of organic chemistry Vol. 71; no. 22; pp. 8516 - 8522
• Main Authors: Saito, Takahiro, Nishimoto, Yoshihiro, Yasuda, Makoto, Baba, Akio
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 27.10.2006; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Organic; Coordination compounds; Exact sciences and technology; Inorganic chemistry and origins of life; Organic chemistry; Physical Sciences; Preparations and properties; Science & Technology; EFFICIENT CATALYST; B(C6F5)-CATALYZED ALLYLATION; RELATIVE REACTIVITIES; BENZYLIC ALCOHOLS; ALLYLIC ALCOHOLS; ACTIVE METHYLENE-COMPOUNDS; GAMMA-LACTOLS; FRIEDEL-CRAFTS ALKYLATION; INDIUM; DEOXYGENATIVE ALLYLATION; Lewis acid; Complexation; Chemoselectivity; Alcohol; Molecular interaction; Organic silane; Acidity; NMR spectrometry; Ketone; Spectral analysis; Organic halogen compounds; Allylation; Chemical coupling; Silicon 29; Acetonitrile; Solvent; Carbon 13; Nucleophile
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo061512k

The combination of InCl3 and Me3SiBr provided an enhanced Lewis acid system that can be used to promote a wide range of direct coupling reactions between alcohols and silyl nucleophiles in non-halogenated solvents, such as hexane or MeCN. The enhanced Lewis acidity of this system was measured by the 13C NMR in terms of the coordination to an alcohol. Moreover, the interaction between Me3SiBr and the In(III) species was revealed by 29Si NMR spectral analysis. Highly chemoselective allylations toward a hydroxyl moiety over ketone and acetoxy ones have been demonstrated.