硼氫化鈉的還原及相關(guān)機(jī)理（課堂PPT）

1、.1金屬氫化物的還原及機(jī)理-NaBH4制作：小魚愛大海.2一：金屬氫化物還原反應(yīng)官能團(tuán)生成官能團(tuán)LiAlH4NaBH4酮仲醇醛伯醇酯伯醇羧酸伯醇酰氯醛注： 表示官能團(tuán)能被還原； 表示官能團(tuán)不能被還原或反應(yīng)很慢兩種主要金屬氫化物的還原特性1參考文獻(xiàn)：1 聞韌 主編 藥物合成反應(yīng) 北京 ：化學(xué)工業(yè)出版社 ，2002. 363.3還原試劑（金屬氫化物）的選擇：NaBH4 R CO2EtROHLiAlH4結(jié)論： 反應(yīng)迅速， 但后處理操作復(fù)雜。.4二、文獻(xiàn)查閱： NaBH4參與的還原反應(yīng)CO2EtR4R1R2R3R4R1R2R3OHNaBH4(6.0 eq) ,MeOH(8mL)THF , 70, 2.

2、0 -4.0 h 88-97（一）、酯的還原1R1, R2,R3,R4 : H, Cl, Br, F, OMeCO2RXXOHNaBH4/ ZnCl2tertiary amine, THF, 2hR = Me, EtX = 2-Br, 2-SCH2Ph ,4- NO2, 4-OH52- 982Reference: 1 Nubia Boechat, Jorge Carlos da Costa ,Jorge de Souza Mendonca, Pedro Santos Mello de Oliveira and MarcusVinicius De Souza . Tetrahedron Lett

3、ers 2004, 45, 6021-6022; 2 R.E. Ten-Brintk, J.Org. Chem. 1987,52, 418 ;.5二、文獻(xiàn)查閱： NaBH4參與的還原反應(yīng)CO2EtNaBH4- I2THF , 70, 0.5 hH2OOH85（一）、酯的還原3Reference: 3Nubia Boechat, Jorge Carlos da Costa ,Jorge de Souza Mendonca, Pedro Santos Mello de Oliveira and MarcusVinicius De Souza . Tetrahedron Letters 2004,

4、45, 6021-6022 ; 4 R .Shundo,Y.Matsubara,K.Nishiguchi,T.Hirashima, Bull.Chem.Soc.Jpn. 65 (1992)530;（二）羧酸的還原R-COOHROHNaBH4-ZnCl2THF ,R= alkyl / aryl70-954.6二、文獻(xiàn)查閱： NaBH4參與的反應(yīng)（二）羧酸的還原5COOHOHNaBH4-ZrCl4THF ,rt, 5h856COOHOHNaBH4-I2THF ,0-2582CO2EtCO2EtCH3(CH2)8COOHNaBH4-I2THF ,0-25CH3(CH2)8CH2OH95Referen

5、ce:5(a) S.Baskaran, V.Gupta, N. Chidambaram, S. Chandrasekaran, J. Chem.Soc. Commun.(1989)903; (b) 6 Nubia Boechat, Jorge Carlos da Costa ,Jorge de Souza Mendonca, Pedro Santos Mello de Oliveira and MarcusVinicius De Souza . Tetrahedron Letters 2004, 45, 6021-6022 ; .7二、文獻(xiàn)查閱： NaBH4參與的還原反應(yīng)RCOOHH2NRH2

6、NOH80-98NaBH4/ H2SO4,THFMeOH , NaOH（三）氨基酸及其衍生物的還原89RCOOHH2NRH2NOH45-94NaBH4-I2,THFrefluxR = alkyl or arylKOHMeOH8 9 (a) Nubia Boechat,Jorge Carlos da Costa ,Jorge de Souza Mendonca, Pedro Santos Mello de Oliveira and MarcusVinicius De Souza . Tetrahedron Letters 2004, 45, 6021-6022 ; (b)R.P.McGeary,

7、 Tetrahedron Lett. 39 (1998) 3319;.8二、文獻(xiàn)查閱： NaBH4參與的還原反應(yīng)PhCH2CNPhCH2CH2NH291NaBH4- ZrCl4THF , rt（四）氰基的還原PhCNNaBH4- I2THFNaOHPhCH2NH272Reference:10 (a) Nubia Boechat,Jorge Carlos da Costa ,Jorge de Souza Mendonca, Pedro Santos Mello de Oliveira and MarcusVinicius De Souza. Tetrahedron Letters 2004,45

8、, 6021-6022; (b) T.Yamakawa, M Masaki, H. Nohira, Bull. Chem. Soc. Jpn. 64 (1991) 2730; (c) C.F.Lane, Chem. Rev. 76 (1976) 773 ; 10.9二、文獻(xiàn)查閱： NaBH4參與的還原反應(yīng)（五）酰氯的還原RCOClRCH2OHR= alkyl / aryl86-98 NaBH4- ZnCl2TMEDAReference: 11Nubia Boechat,Jorge Carlos da Costa ,Jorge de Souza Mendonca, Pedro Santos Mello de Oliveira and MarcusVinicius De Souza. Tetrahedron Letters 2004,45, 6021-6022; .10四、氫負(fù)離子還原機(jī)理BHHH