Gold(I)-Catalyzed Ring Expansion of Cyclopropanols and Cyclobutanols

• Published in: Journal of the American Chemical Society Vol. 127; no. 27; pp. 9708 - 9709
• Main Authors: Markham, Jordan P, Staben, Steven T, Toste, F. Dean
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 13.07.2005; Amer Chemical Soc
• Subjects: Butanols - chemistry; Catalysis; Chemistry; Chemistry, Multidisciplinary; Cyclization; Ethers, Cyclic - chemistry; Exact sciences and technology; Gold - chemistry; Kinetics and mechanisms; Ligands; Molecular Structure; Organic chemistry; Physical Sciences; Reactivity and mechanisms; Science & Technology; CATALYZED REARRANGEMENTS; CATIONIC GOLD(I) COMPLEXES; CYCLIZATION; Stereoselectivity; Catalytic reaction; Gold Complexes; Catalyst selectivity; Tertiary alcohol; Reaction mechanism; Transition metal Complexes; Complex catalyst; Experimental study; Catalyst activity; Monocyclic compound; Ring expansion
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja052831g

The rearrangement of 1-alkynyl cyclobutanols and cyclopropanols to alkylidene cycloalkanones catalyzed by cationic triarylphosphine gold(I) complexes is described. The reaction tolerates terminal alkynes as well as alkyl, aryl, and halo-substitution at the acetylenic position and stereoselectively provides a single olefin isomer. The gold(I)-catalyzed rearrangement is stereospecific with regard to substituents on the ring, thus providing a practical method for the stereoselective synthesis of highly substituted cyclopentanones from cyclopropanols. The reaction stereoselectively provides a single olefin isomer and is stereospecific with regard to substituents on the ring via sequential gold(I)-catalyzed ring expansion reactions.