✍ Scribed by Robert A Moss; Song Xue; Wei Ma; Huarong Ma
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The signature intramolecular reaction of an acyloxycarbene is 1,2-acyl migration to give a 1,2-dione; the 1,2-acetyl shift of phenylacetoxycarbene (1) to dione 2 (kAc = 1.3 x 105 s -l) is an archetypal example. ~-3
The analogous benzoyl shift of phenylbenzoyloxycarbene (3) to benzil occurs with kphco = 6.
📜 SIMILAR VOLUMES
Intramolecular 1,2-H shifts of alkyl or alkylchlorocarbenes are often very rapid making it difficult to relate structure with reactivity in terms of absolute rate constants. For example, k H in hydrocarbon solvents at 25 °C for Me2CHCCI, PhCH(Me)CC1, or EtCC1 exceeds l0 s s-~, 1' 2 while k, for PhCH
Abstrack Two examples of the title maction = described. While the kinetically p&end pathway for 2 utilizes tlw vinyl substituent, that far 16 skirts this option cmnpletely. To a great extent, these biases are a function of the sauctud features inherent to these aicohoir. Although oxy-cope rearrange
Unsymmetrical bis-allyl silylketene acetals derived from cyclohexenones undergo regio-and stereoselective Ireland Claisen rearrangements to afford alkylidene cyclohexenes in good yield.