Phosphane Sulfide/Octacarbonyldicobalt-Catalyzed Pauson – Khand Reaction Under an Atmospheric Pressure of Carbon Monoxide

Abstract

Einen leichten Zugang zu Cyclopentenonen bieten katalytische, intra‐ und intermolekulare Pauson‐Khand‐Reaktionen in Gegenwart von Octacarbonyldicobalt und Tributylphosphansulfid (siehe Schema). Im Unterschied zu anderen Reaktionen dieses Typs verlaufen die hier beschriebenen unter milden Bedingungen (70 °C, 1 atm CO), und handelsübliches [Co2(CO)8] kann ohne weitere Reinigung als Katalysator verwendet werden.

Regioselectivity, Stereoselectivity and Catalysis in Intermolecular Pauson-Khand Reactions: Teaching an Old Dog New Tricks

“…cyclohexylamine, tributylphosphanesulfide) as was independently reported by Sugihara, 93 Krafft, 94 and Hashimoto. 95 Catalytic reactions were also possible by microwave irradiation according to results by Groth. 96,97 Very recently, the cyclobutadiene equivalent 146 was successfully employed in catalytic cocyclizations by Gibson (Scheme 59).…”

Advances in the Pauson-Khand Reaction: Development of Reactive Cobalt Complexes

“…Suppression of the redox process, which decomposes dicobalt octacarbonyl, is a key to bring about a fruitful result. In this sense, most of the known methods for the catalytic Pauson–Khand reaction by the addition of a Lewis base, such as phosphites,13a ethers,13b, 13d amines,13e, 13i and phosphane sulfides,13g may activate dicobalt octacarbonyl and stabilize the active catalysts sterically and electronically by their coordination.…”

Total Synthesis of (−)‐Jiadifenin

“…Upon dihydroxy deprotection15 and selective silylation of the secondary hydroxy group at C7, the 13 a / 13 b mixture (derived from ( Z )‐ 6 , as mentioned above) was converted into enynes 14 a / 14 b in 51 % combined overall yield (Scheme ). Treatment of the 14 a / 14 b mixture with [Co 2 (CO) 8 ] effected an IMPKR8d to produce tricyclic enone 4 (67 %) and epi ‐ 4 (6 %) along with a trace amount of enyne/Co 2 (CO) 6 complexes. Whereas 14 a furnished 4 and epi ‐ 4 , lactone 14 b only resulted in the formation of the enyne/Co 2 (CO) 6 complex without further cyclization.…”