Calcium-Mediated Catalytic Synthesis of 1-(Diorganylamino)-1,4-diphenyl-4-(diphenylphosphanyl)buta-1,3-dienes

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• 作者：Fadi M. Younis ; Sven Krieck ; Tareq M. A. Al-Shboul ; Helmar Görls ; Matthias Westerhausen
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：May 2, 2016
• 年：2016
• 卷：55
• 期：9
• 页码：4676-4682
• 全文大小：356K
• 年卷期：0
• ISSN：1520-510X

文摘

The hydroamination of diphenylbutadiyne with 1 equiv of the secondary amines HNRR′ (R/R′ = Ph/Ph, Ph/Me, and pTol/Me) in the presence of catalytic amounts of the tetrakis(amino)calciate K₂[Ca{N(H)Dipp}₄] (Dipp = 2,6-diisopropylphenyl) yields the corresponding 1-(diorganylamino)-1,4-diphenylbut-1-ene-3-ynes as a mixture of E/Z isomers. These tertiary alkenylamines react with diphenylphosphane to form RR′N–C(Ph)═CH–CH═C(Ph)–PPh₂ [R/R′ = Ph/Ph (1), Ph/Me (2), and pTol/Me (3)] in the presence of catalytic amounts of [(THF)₄Ca(PPh₂)₂] or of the same calciate K₂[Ca{N(H)Dipp}₄]. Whereas the hydroamination is regio- (amino group in 1-position) but not stereoselective (formation of E and Z isomers), this second hydrofunctionalization step is regio- (phosphanyl group in 4-position) and stereoselective (only E isomers are formed), finally leading to mixtures of (E,E)- and (Z,E)-1-(diorganylamino)-1,4-diphenyl-4-(diphenylphosphanyl)buta-1,3-dienes.