Low-Valent Titanium-Mediated Stereoselective Alkylation of Allylic Alcohols

• Published in: Journal of the American Chemical Society Vol. 130; no. 47; pp. 15997 - 16002
• Main Authors: Lysenko, Ivan L, Kim, Keunho, Lee, Hyung Goo, Cha, Jin Kun
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 26.11.2008; Amer Chemical Soc
• Subjects: Alkenes - chemistry; Alkylation; Chemistry; Chemistry, Multidisciplinary; Cross-Linking Reagents - chemistry; Ether - chemistry; Molecular Structure; Physical Sciences; Propanols - chemistry; Science & Technology; Stereoisomerism; Titanium - chemistry; CARBON BOND FORMATION; UNSATURATED-COMPOUNDS; ALKENES; SUBSTITUTED 1,4-DIENES; ETHYLATION; DIASTEREOSELECTIVE SYNTHESIS; ETHYLMAGNESIUM BROMIDE; HOMOALLYLIC ALCOHOLS; COMPLEXES; CARBOXYLIC ESTERS
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja806440m

We have developed low-valent titanium-mediated 1,3-transpositive cross-coupling reactions of acyclic and cyclic allylic alcohols for the stereoselective introduction of ethyl, 2-silylethyl, 2-phenethyl, and alkenyl groups. Cross-coupling of an allylic alcohol with a vinylsilane or styrene derivative is particularly noteworthy, as an efficient cross-selective coupling of two alkenes has been elusive. The stereochemistry of the cross-coupling alkylation is consistent with syn addition/β-elimination.