Nickel-catalysed reactions allylic compounds

G. P. Chiusoli and L. Cassar Angew. Chem. 79,177 (1967) Angew. Chem. Int. Ed. Engl. 6, 124 (1967) Nickel-catalysed reactions of allyl halides and related compounds 10 (55) ... 

Bis[(dimethylisopropoxysilyl)methyl]zinc (74) has proven to be a valuable reagent in the nickel-catalysed cross-coupling reactions with alkenylsulfoximines, giving allylic silanes with complete retention of configuration. An X-ray crystal structure determination of 74 showed this compound to exist in the solid state as a coordination polymer (Figure 41). In 74, in addition to the two covalent Zn—C bonds [Zn—C(l) 1.953(7)... 

The kinetics and mechanism of nickel-catalysed olefin hydrocyanation have been reported , and the addition of DCN to cyclohexa-1,3-diene catalysed by [Ni (p 0Ph 3 )i ] is found to occur with cis-stereochemistry indicating cis-migration of coordinated cyanide in the intermediate ir-allyl complex. The reactions of various organic bromides RBr (R Ph, PhCH=CH, allyl, MeCH=CHCH2) with a mixture of bicycloheptene or bicycloheptadiene and alkynes R C=CH (R =Ph, hexyl, etc) catalysed by Ni(0) or Pd(0) complexes produce bicyclic compounds such as (55) . PhCH=CHBr reacts with bicyclo [2.2.1]hept-2-ene and R2NH (R2 = (CH2), (CH2)5,... 

Carbonylative cycloaddition of allyl bromides and acetylenes in methanol in the presence of nickel tetracarbonyl results in the formation of cyclopentenones. For instance, 3-bromocyclopentene and methyl but-2-ynoate afford the diester 493, the halogen atom being replaced by the methoxycarbonyl group. Nickel tetracarbonyl also catalyses the reaction of l-(bromomethyl) cycloalkenes 494 of ring size 5-8 with methyl but-2-ynoate in methanol to yield the spiro-compounds 495 (equation 54). ... 

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