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1.4.4.15.1 Rearrangement of 1-(Alk-1-ynyl)cyclopropanols

DOI: 10.1055/sos-SD-001-00322

Malacria, M.; Aubert, C.; Renaud, J.-L.Science of Synthesis, (20011518.

The rearrangement of 1-(alk-1-ynyl)cyclopropanols 106 to cyclopent-2-en-1-ones proceeds on complexation of their alkynyl part with octacarbonyldicobalt(0) (83).[‌386‌] When the compounds 106 were treated with 1.1 equivalents of complex 83 in tetrahydrofuran at room temperature, complete formation of the corresponding complex occurred. These complexes remained unchanged at room temperature, but, when the solutions were heated to reflux, the corresponding cyclopentenones were obtained in good yields (Scheme 93). The use of ethereal solvents (e.g., THF, DME) generally favored this rearrangement. Various alkynyl substituents (alkyl, aryl, trialkylsilyl) and even those containing functional groups (alkylsulfanyl, tert-butyldimethylsiloxy, hydroxy) can be employed in this reaction.[‌387‌] In the case of the reactions of 1-(alk-1-ynyl)cyclopropanols with an alkyl substituent on the cyclopropane ring, either 4- or 5-substituted cyclopent-2-en-1-ones could be selectively obtained by appropriate choice of stereochemistry and protective group of the substrates (Scheme 93).

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