Allyl cyanides, reactions with alkyne

Phenylacetonitriles can be induced to undergo Michael reactions with unactivated alkenes. For example, propenylarenes, formed in situ from allylarenes, react with phenylacetonitriles to form 3-aryl-l-cyano-2-methyl-l-phenylpropanes (70-98%) [3] by a procedure analogous to 6.4.1.B, Similarly, the nitriles react with alkynes giving allyl cyanides (80-95%) [38]. 

Reaction with an amine, AIBN, CO and a tetraalkyltin catalyst also leads to an amide.Benzylic and allylic halides were converted to carboxylic acids electroca-talytically, with CO and a cobalt imine complex. Vinylic halides were similarly converted with CO and nickel cyanide, under phase-transfer conditions.Allylic (9-phosphates were converted to allylic amides with CO and ClTi=NTMS, in the presence of a palladium catalyst. Terminal alkynes were converted to the alkynyl ester using CO, PdBr2, CuBr2 in methanol and sodium bicarbonate. ... 

Nitrites. Allylic cyanides are formed from the acetates or carbonates in (PhsPjaPd-catalyzed transformations. Intramolecular cyanosilylation of alkynes provides a way of controlled functionalization of such compounds using a tether tac- a-Cyano selenides are products from SnCU-catalyzed reaction of diselenoacetals with MeiSiCN. Seleno-ortho esters also exchange one seleno group for the cyanide. ... 

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,... 

Among a host of other phosphine-catalysed reactions in which the initial step is the formation of a reactive phosphoniobetaine intermediate by addition to a carbon-carbon double or triple bond are intramolecular cyclisations leading to benzobicyclo[4,3,0]-compounds, " cyclic ethers " and lactones,and a great many intermolecular reactions, e.g., a [3 -b 3]-annulation of modified t-butyl allylic carbonates and alkylidenemalonitriles to give cyclohexenes,phosphine- (and fluoride)- catalysed routes to 1,4-benzothiazepines from cyclic sulfenamides and alkynes, a [4- -3]-annu-lation of allylic carbonates with methyl coumalate to give functionalised bicyclo[3.2.2]nonadienes, the a-carbon addition of cyanide ion, generated in situ from cyanohydrins, to activated alkynes, and a stereoselective... 

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