Catalysed Additions to Alkenes, Alkynes and Telomerisation Reactions

10 Catalysed Additions to Alkenes, Alkynes and Telomerisation Reactions 

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, 

Telomerisation of formamide with buta-1,3-diene with a catalyst derived from PdS+/pph3/Et3Al/CF3C02H gives 16.8% 

CH2=CH(CH2)3CH=CHCH2NHCH0 and CH2=CH(CH2)3CH(NHCHO)CH=CH2 (83 17)S2i. Telomerisation of isoprene with cyclopentanone or cyclohexanone in the presence of H2O and Pd(0)/PR3 complexes gives the tail-to-tail products (57 n = 0, 1)S22 fhe arylation of activated alkenes with aryl chlorides catalysed by Pd(OAc)2/PR3 (R = Ph, p-MeCgH ) is accelerated by electron-withdrawing substituents in the aryl chlorideS23. 

---