Wolff cyclohexene

The reaction of cyclohexene with the diazopyruvate 25 gives unexpectedly ethyl 3-cyclohexenyl malonate (26), involving Wolff rearrangement. No cyclo-propanation takes place[28]. 1,3-Dipolar cycloaddition takes place by the reaction of acrylonitrile with diazoacetate to afford the oxazole derivative 27[29]. Bis(trimethylstannyl)diazomethane (28) undergoes Pd(0)-catalyzed rearrangement to give the A -stannylcarbodiimide 29 under mild conditions[30]. 

Cyclobutanones. Irradiation of 1 in the presence of cyclohexene produces the cyclobutanone 2 rather than the cyclopropane 3, as originally believed. This reaction involves a Wolff rearrangement of the initially formed carbene (a) to a ketene (b), which undergoes regio- and stereoselective cycloaddition to the olefin. 

The first total synthesis of the antibiotic acanthodoral (1) 118 has been achieved from 3-methyl-2-cyclohexen-l-one in 19 steps in 2.1% overall yield. This synthesis involves the use of a Pd-ene reaction in the presence of CO to form the endocyclic alkene 116, a nonreductive acyl radical cyclization and ring contraction by the Wolff rearrangement of ll ." ... 

However, photolysis of diazoketone 218 in cyclohexene affords adduct 219, presumably because of the low mobility of an amide in the Wolff rearrangement (Scheme 41)." ... 

Cyclohexene is converted to cyclohexanol upon treatment with aqueous acid (acid-catalyzed hydration). Cyclohexanol is oxidized to cyclohexanone upon treatment with a strong oxidizing agent. Upon treatment with hydrazine in acid-catalyzed conditions, cyclohexanone is converted into the corresponding hydiazone. A WolfF-Kishner reduction then gives cyclohexane. 

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