Hydroalumination of diazo and azido compounds:An Al-H addition to end-on nitrogen of substrates  

作　　者：CHU ChenHui1,YANG Ying1,2 & ZHU HongPing1 1State Key Laboratory of Physical Chemistry of Solid Surfaces National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China 2School of Chemistry and Chemical Engineering,Central South University,Changsha 410083,China 

出　　处：《Science China Chemistry》2010年第9期1970-1977,共8页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China (20842006, 20972129, and 20902112);China Postdoctoral Science Foundation (20090460748);the Fund for New Teacher of Higher Education (200803841012);the Project Sponsored by SRF for ROCS, SEM (2009060011500466)

摘　　要：This paper reports the reactions of a monomeric aluminum dihydride LAlH2(L = HC[C(Me)N(Ar)]2,Ar = 2,6-i-Pr2C6H3) with diazo,azido,and terminal alkyne compounds.The reaction of LAlH2 with N2CH(SiMe3) and N3(1-Ad) occurred through an Al-H addition to end-on nitrogen to yield respective compounds LAl[N(H)N = CH(SiMe3)]2(1) and LAl[N(H)N=N(1-Ad)]2(2),while the reaction of LAlH2 with PhC≡CH occurred through a stepwise deprotonation to yield LAlH(C≡CPh)(5) and LAl-(C≡CPh)2(6),respectively.2 further reacted by N2-release to yield LAl[NH(1-Ad)][N(H)N=N(1-Ad)](3) and LAl[NH-(1-Ad)]2(4) upon the increased temperature treatment.Compounds 1-6 have been fully characterized,revealing novel reactivity patterns of LAlH2 toward different substrates under the steric influence from the bulky L ligand at Al.This paper reports the reactions of a monomeric aluminum dihydride LAlH2(L = HC[C(Me)N(Ar)]2,Ar = 2,6-i-Pr2C6H3) with diazo,azido,and terminal alkyne compounds.The reaction of LAlH2 with N2CH(SiMe3) and N3(1-Ad) occurred through an Al-H addition to end-on nitrogen to yield respective compounds LAl[N(H)N = CH(SiMe3)]2(1) and LAl[N(H)N=N(1-Ad)]2(2),while the reaction of LAlH2 with PhC≡CH occurred through a stepwise deprotonation to yield LAlH(C≡CPh)(5) and LAl-(C≡CPh)2(6),respectively.2 further reacted by N2-release to yield LAl[NH(1-Ad)][N(H)N=N(1-Ad)](3) and LAl[NH-(1-Ad)]2(4) upon the increased temperature treatment.Compounds 1-6 have been fully characterized,revealing novel reactivity patterns of LAlH2 toward different substrates under the steric influence from the bulky L ligand at Al.

关 键 词：hydroalumination bulky aluminum hydride multiple-bond molecule Al–H ADDITION 

分 类 号：O621.25[理学—有机化学]