有機合成化学協会誌
Online ISSN : 1883-6526
Print ISSN : 0037-9980
総説および総合論文
ハーフサンドイッチ型希土類錯体触媒を用いた有機合成反応の開発
鈴木 俊彰張 文雄西浦 正芳侯 召民
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2009 年 67 巻 5 号 p. 451-464

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Half-sandwich rare-earth metal alkyl complexes bearing the silylene-linked cyclopentadienyl-amido ligand can serve as efficient catalyst precursors for the catalytic (Z)-selective head-to-head dimerization of terminal alkynes to give the corresponding conjugated (Z)-enynes, which represents the first example of exclusive formation of a (Z)-enyne compound in the dimerization of an aromatic alkyne. They also work for the catalytic addition of terminal alkyne C-H, amine N-H, and phosphine P-H bonds to carbodiimides (R'N=C=NR'), to give a new family of propiolamidines, guanidines, and phosphaguanidines, respectively, some of which were difficult to prepare previously. The half-sandwich rare-earth-catalyzed cross-coupling of terminal alkynes with isocyanides affords selectively the corresponding (Z)-1-aza-1, 3-enyne pro-ducts for the first time. Mechanistic aspects of these catalytic processes are also described.

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© 2009 社団法人 有機合成化学協会
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