Key
Wordr cychc unsaturated a-Dlaro ketones, IMhodtum tetraacetate, Carbon-hydrogen Inserttoo, Cyclopropanahon. Selectlvlty Abstractz Dlazo carbonyl compounds, when calalyzcd by dlrhodmm tetraacetate, ~mcrt to allyhc po5ltton MS phenomenon was explmted m cychc rystems 3d, Sd, 5& and IO The rcactn4y toward allyhc tnsertlon I.S corroborated by the unexpected six-memhered nng cyclvatlon m the transformatton 5g+9 'OAc \OAC 1 2
Artcr this prtmary obscrvatlon It was reported that m the dccomposltlon of acychc unsaturated dlazoketones, the carbon-hydrogen bond rnsertlon occurs to a greater extent than the cyclopropanatron process and the electron wlthdrawmg groups (e g vmyl, phenyl,%) reduce the reactivity of the allyhc carbonhydrogen bond when compared wtth the ahphatlc one 3
The different hehavrour of cychc and acychc unsaturated dlazo-kctoncc prompted us to prepare scvrral cyclic models m order to obtam more mformatlon on the sclcctlvlty of the c.ychlatlon process Dlazo-ketone 3d was prepared to test the influence of the dlazocarbonyl chatn length on the selectlvrty of the mtramolecular myertlon process versus 1 The treatment of wrescenol B dlacctate 3aw1th osmium