Catalytic Cyclopropanation of Alkenes via (2-Furyl)carbene Complexes from 1-Benzoyl-cis-1-buten-3-yne with Transition Metal Compounds

• Published in: Journal of organic chemistry Vol. 69; no. 5; pp. 1557 - 1564
• Main Authors: Miki, Koji, Yokoi, Tomomi, Nishino, Fumiaki, Kato, Yumiko, Washitake, Yosuke, Ohe, Kouichi, Uemura, Sakae
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 05.03.2004; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Organic; Exact sciences and technology; Heterocyclic compounds; Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives; Kinetics and mechanisms; Organic chemistry; Physical Sciences; Preparations and properties; Reactivity and mechanisms; Science & Technology; FISCHER CARBENE COMPLEXES; SKELETAL REORGANIZATION; ENYNE METATHESIS; MECHANISM; DIAZO-COMPOUNDS; GENERATION; SPECTROSCOPIC OBSERVATION; ALKYNES; DERIVATIVES; CYCLIZATION; Cationic complex; Transition element complexes; Cyclopropane derivatives; Acetylenic compound; Chemoselectivity; Chromium Carbonyl Complexes; Furan derivatives; Palladium complex; Oxygen heterocycle; Tetrahydrofurane; Carbene; Vinyl complex; Chemical synthesis; Rhodium complex; Catalytic reaction; Regioselectivity; Carbenoid; Dienic compound; Ketone; Platinum complex; Enynic compound; Cyclopropanation; Conjugated compound; Ethylenic compound; Ruthenium complex; Catalyst selectivity; Transition metal Carbonyl Complexes; Complex catalyst; Experimental study; Reaction mechanism; Catalyst activity
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo0352732

The reaction of alkenes with conjugated ene-yne-ketones, such as 1-benzoyl-2-ethynylcycloalkenes, with a catalytic amount of Cr(CO)5(THF) gave 5-phenyl-2-furylcyclopropane derivatives in good yields. The key intermediate of this cyclopropanation is a (2-furyl)carbene complex generated by a nucleophilic attack of carbonyl oxygen to an internal alkyne carbon in π-alkyne complex or σ-vinyl cationic complex. A wide range of late transition metal compounds, such as [RuCl2(CO)3]2, [RhCl(cod)]2, [Rh(OAc)2]2, PdCl2, and PtCl2, also catalyzes the cyclopropanation of alkenes with ene-yne-ketones effectively. When the reactions were carried out with dienes as a carbene acceptor, the more substituted or more electron-rich alkene moiety was selectively cyclopropanated with the (2-furyl)carbenoid intermediate.