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Mechanism, reactivity, and selectivity of nickel-catalyzed [4 + 4 + 2] cycloadditions of dienes and alkynes.


ABSTRACT: Density functional theory (DFT) calculations with B3LYP and M06 functionals elucidated the reactivities of alkynes and Z/E selectivity of cyclodecatriene products in the Ni-catalyzed [4 + 4 + 2] cycloadditions of dienes and alkynes. The Ni-mediated oxidative cyclization of butadienes determines the Z/E selectivity. Only the oxidative cyclization of one s-cis to one s-trans butadiene is facile and exergonic, leading to the observed 1Z,4Z,8E-cyclodecatriene product. The same step with two s-cis or s-trans butadienes is either kinetically or thermodynamically unfavorable, and the 1Z,4E,8E- and 1Z,4Z,8Z-cyclodecatriene isomers are not observed in experiments. In addition, the competition between the desired cooligomerization and [2 + 2 + 2] cycloadditions of alkynes depends on the coordination of alkynes. With either electron-deficient alkynes or alkynes with free hydroxyl groups, the coordination of alkynes is stronger than that of dienes, and alkyne trimerization prevails. With alkyl-substituted alkynes, the generation of alkyne-coordinated nickel complex is much less favorable, and the [4 + 4 + 2] cycloaddition occurs.

SUBMITTER: Hong X 

PROVIDER: S-EPMC4275152 | biostudies-literature | 2014 Dec

REPOSITORIES: biostudies-literature

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Mechanism, reactivity, and selectivity of nickel-catalyzed [4 + 4 + 2] cycloadditions of dienes and alkynes.

Hong Xin X   Holte Dane D   Götz Daniel C G DC   Baran Phil S PS   Houk K N KN  

The Journal of organic chemistry 20141107 24


Density functional theory (DFT) calculations with B3LYP and M06 functionals elucidated the reactivities of alkynes and Z/E selectivity of cyclodecatriene products in the Ni-catalyzed [4 + 4 + 2] cycloadditions of dienes and alkynes. The Ni-mediated oxidative cyclization of butadienes determines the Z/E selectivity. Only the oxidative cyclization of one s-cis to one s-trans butadiene is facile and exergonic, leading to the observed 1Z,4Z,8E-cyclodecatriene product. The same step with two s-cis or  ...[more]

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