Metal-Triflate-Catalyzed Synthesis of Polycyclic Tertiary Alcohols by Cyclization of γ-Allenic Ketones

• Published in: Angewandte Chemie (International ed.) Vol. 53; no. 16; pp. 4177 - 4180
• Main Authors: Diaf, Ilhem, Lemière, Gilles, Duñach, Elisabet
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 14.04.2014; WILEY‐VCH Verlag; Wiley
• Subjects: Alcohols - chemical synthesis; Alkadienes - chemistry; allenes; bismuth; Bismuth - chemistry; Catalysis; Chemistry; Chemistry, Multidisciplinary; Cyclization; cyclizations; homogeneous catalysis; Ketones - chemical synthesis; Molecular Structure; Physical Sciences; Science & Technology; synthetic methods; LEWIS-ACID; ALDEHYDES; ENE REACTIONS; CARBONYL UNITS; BUTYROLACTONES; cyclizations; allenes; CYCLOPENTANOLS; BISMUTH(III) TRIFLATE; homogeneous catalysis; DIELS-ALDER REACTION; CYCLOISOMERIZATIONS; EFFICIENT; synthetic methods; bismuth
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201310724

It has been established that bismuth(III) triflate catalyzes the cyclization of γ‐allenic ketones under mild reaction conditions. This reaction allows the selective formation of polycyclic tertiary alcohols from cyclic ketone derivatives. The resulting dienols can engage in stereoselective cycloadditions to efficiently afford complex polycyclic systems. Simply complex: The described catalytic carbonyl‐ene reaction is efficiently performed under mild reaction conditions by using only 1 mol % of bismuth(III) triflate, thus affording functionalized molecular scaffolds. Complex polycyclic structures with a defined stereochemistry have been synthesized by using the carbonyl‐ene products in a subsequent hydroxy‐directed Diels–Alder reaction.