有机硼作中间体的合成反应 (53页).doc

第五章 有机硼作中间体的合成反应 B : 2s22p1  1. 极性：  ＋ B  － H  RCH  CH2 +  B  H  RCH  CH2  RBH2  R2BH R3B  H B 2. 烃基负离子源泉  R  R  R  B + :A  B  A B A  形成C－O，C－X，C－N，C－C键等 3.自由基源泉 R B + O2 R + B O O 一．有机硼试剂的制备  1．烃基硼烷的制备  3NaBH 4  +  4BF3Et2O  THF  2B2H6 + 3NaBF4 + 4Et2O  2NaBH4 + 2H  THF  B2H6 +  2H2  + 2Na  RCH  CH2  + B2H6  RCH2CH2BH2  (1)  RCH2CH2BH2 + RCH  CH2  (RCH2CH 2)2BH  (2)  (RCH2CH2)2BH  + RCH  CH2  (RCH2CH2)3B  (3)  反应速度：（1）（2）（3） 商业试剂： BH3.SMe2 重要硼烷试剂：  H3C H3C  C  C  H CH3  +  B2H6  H3C  CH3 CH3 C C H H  BH 2  Secondary isoamyl borane Sia2BH  H3C H3C C  C  CH3 + CH3  B2H6  CH3 CH3 HC C BH2 CH3 CH3 thexyl borane BH2 1  8  9  7  6  H B + B2H6  2 BH  5  BH  3  4 9-borabicyclo[3.3.1]nonane 9-BBN 其它硼试剂  （1） H3B SMe2  +  2Cl3B SMe2  3Cl2BH  SMe2  2H3B  SMe2  +  Cl3B  SMe2  3ClBH2 SMe2  （2）  OH  O  OH  + H3B THF  O  BH  +  H2  （3）  B  +  H  B  3-蒎基-9-硼[3.3.1]壬烷 NaBH4/I2体系  THF  H3B THF  2NaBH4 + I2 diglyme  B2H6  2NaI + H2  Ph  Ph  N(Et)2Ph  H3B N(Et)2Ph  H3B N(Et)2Ph  N H  OH  N Ph  Ph B O  H CBS试剂 2.芳基硼化合物制备: Zhu, L.; Duquette, J.; Zhang, M. J. Org. Chem. 2003, 68, 3729. John Cody and Christoph J. Fahrni* Tetrahedron 2004 , 60, 11099–11107. Wei Zhu and Dawei Ma Formation of Arylboronates by a CuI-Catalyzed Coupling Reaction of Pinacolborane with Aryl Iodides at Room Temperature ORGANIC LETTERS， 2006，261-263. 3. 烯基硼烷制备:  R2B  H  R2BH + HC CR1  H R1 Robert S. Coleman,* Xiaoling Lu, and Isabelle Modolo J. AM. CHEM. SOC., 2007, ASAP Takai, K.; Shinomiya, N.; Kaihara, H.; Yoshida, N.; Moriwake, T. Synlett 1995, 963. Andrei S. Batsanov, Jonathan P. Knowles, and Andrew Whiting* J. Org. Chem. 2007, 72, 2525-2532 1979 Nobel Prize Born in London, Professor Brown came to the USA at the age of two. He attended Wright Junior College prior to enrolling at the University of Chicago, where he completed his BS in 1936 and his PhD in 193