现代有机合成课件5-有机硼

1、第五章第五章 有机硼作中间体的合成反应有机硼作中间体的合成反应 B : 2s22p11. 极性极性： BHRCHCH2+BHRCHCH2HBRBH2R2BH R3B2. 烃基负离子源泉烃基负离子源泉 3.3.自由基源泉自由基源泉BR+O2R+B O O形成形成CO，CX，CN，CC键等键等 BR+:ABRB ARA一有机硼试剂的制备一有机硼试剂的制备1烃基硼烷的制备烃基硼烷的制备 3NaBH4+4BF3Et2OTHF2B2H6+3NaBF4+ 4Et2O2NaBH4+2HTHFB2H6+2Na2H2RCHCH2+ B2H6RCH2CH2BH2(1)(RCH2CH2)2BH+ RCHCH2(RC

2、H2CH2)3B(3)RCH2CH2BH2+ RCHCH2(RCH2CH2)2BH(2)反应速度：（反应速度：（1 1） （2 2） （3 3） 商业试剂：商业试剂： BH3.SMe2重要硼烷试剂重要硼烷试剂： CCH3CH3CHCH3+B2H6BHSecondary isoamyl boraneSia2BHH3CCHCH3CHCH32CCH3CH3CCH3CH3+B2H6HCCCH3CH3CH3CH3BH2thexyl boraneBH2+B2H6BH123456789HB9-borabicyclo3.3.1nonane9-BBNBH其它硼试剂其它硼试剂 H3BSMe2+2Cl3B SMe2

3、3Cl2BHSMe22H3BSMe2+SMe2SMe2Cl3B3ClBH2OHOH+H3B THFOOBH+H2（1）（2）（3）+BHB3-蒎基-9-硼3.3.1壬烷Wei Zhu and Dawei MaFormation of Arylboronates by a CuI-Catalyzed Coupling Reaction of Pinacolborane with Aryl Iodides at Room TemperatureORGANIC LETTERS， 2006，261-263.Born in London, Professor Brown came to the USAa

4、t the age of two. He attended Wright Junior Collegeprior to enrolling at the University of Chicago, where he completed his BS in 1936 and his PhD in 1938. His graduate studies under the guidance of H. I. Schlesinger were focused on the reaction of diborane with carbonyl compounds. After studying fre

5、e-radical reactions in Chicago in 1939 with M. S. Karasch, he became Schlesingers assistant with the rank of instructor.During his career, he supervised 163 PhD students and 190 postdoctoral fellows. He also authored 8 books and nearly 1300 scientific publications.1979 Nobel Prize二碳二碳- -氢键的形成氢键的形成 1

6、还原反应还原反应在室温下能使在室温下能使 等还原等还原 C=O，COOR,COOH,CN作还原剂选择性更好作还原剂选择性更好 R2BH, RBH2可使可使 C=O C=O 还原，但还原，但COOR,COCl,COOH均不均不还原。还原。 BH2例例2. 硼氢化反应硼氢化反应CCHR2R1+B2H6CHCHR2RR1BOAcHHOAcCHCHR2RR1HRRCCR+Sia2BHCCRHRBSia2HOAcCCRHRH(顺式）Da-Ming Du, Tao Fang, Jiaxi Xu, and Shi-Wei Zhang Org. Lett. 2006, 8(7), 1327. 三碳氧键的形成三

7、碳氧键的形成 RCHCH2+B2H6(RCH2CH2)3BH2O2/NaOH3RCH2CH2OHBR+O O HBROO HB OR+OHB OH+B O+ ROHOHROHCH3BH2BHCH31.HOAc2.H2O2/NaOHHOHCH3D()-新薄荷醇D（）rHHHBHCH3HHHCH3BSLMHMLSHCH3H3CHCCH3CCH3HHBHEtH3CHHO2BHCH3HHH3CH2O2NaOHHO CCH3HEtR-2-丁醇99.1ee2BCH3CH2CH3H四碳卤键的形成四碳卤键的形成RCHCH2(RCH2CH2)3BBr2NaOCH3NaI氯胺TRCH2CH2BrRCH2CH2IB

8、BrRRRBrBBrRRRBrOCH3B OCH3RR+RBr RCCHSia2BHCCRHHBSia2Br2反式加成CCRHHBSia2BrBrCCRHHBrBrBSia2CCRHHBr（E型）HOHCCRBrHHBrBSia2HOHCCRHBrH（Z型)五碳碳键的形成五碳碳键的形成 1烃化反应烃化反应 R3B+CHCBrOR2R1t-BuOKCHCOR2R1Rt-BuOHCH3+BHCH3BBrCH2COOEtt-BuOKCH3CH2CH2OOEt例例CHCBrOR2R1t-BuOKCCBrOR2R1R3BRBRCRR1BrCR2OBCRRRCR2R1OCHCRR1R2O+BRROBut-

9、BuOH21，4加成反应加成反应CH2CHCOOR1R3B+(PhCOO)2RCH2CH CR1OBR2H2ORCH2CH2CORR3BO2RR+CH2CHCOR1RCH2CH CR1OR3BRCH2CH CR1OBR2+R例例 +BrMgBOO1.HOOH2.BH23. HOAc4. HCl/H2OOHHZ-型BrB3羰基化反应羰基化反应（1）合成叔醇）合成叔醇R3B+COR3CBOH2O2NaOHR3COH100125 0C常压R3B+CORBRRCORBRRCOBORRRRRRBO例例BCB2H61. CO2. H2O2/NaOHOH（2）合成酮）合成酮R3B+CO +H2OBCOH O

10、HRRRH2O2NaOHORRBCOH OHRRH2O2NaOHOR1R2BH2BR1HBR1R2COH2OBCOH OHRRRBORRRH2O例例BH2CH3CHCHCH3+BCH3HOCOCH3nBCH3OnO1. CO/H2O2. H2O2/NaOHCH3OnOOB1. CO/H2O2. H2O2/NaOHClHSMe3BClKBH(OPr-i)3BHOAcBOAcOHO1. PyCrO3Cl2. NaOHO（3）合成醛和伯醇）合成醛和伯醇+BRBCO+LiAlH(OCH3)3HROAl(OCH3)3NaOH/H2ONaOH/H2O2RCH2OHRCHO六与炔化物反应六与炔化物反应R2B

11、H+ HCCR1HR2BHR1I2NaOHBrCNRHHR1HHRR1BrCNHR2BHR1RBrBHR1HRNCRBrBHR1HRNCHHRR1HR2BHR1I2IHBHR1RRIRIBHR1HRIOHBIHR1RHRIRHHR1OHHBBr2 SMe2BBr2 SMe21/4 LiAlH4BHBr SMe2HCCC10H21-nHBHC10H21-nBrNaOCH3HBHC10H21-nOCH3I2/NaOCH3ArCO3HOHH七与炔基锂反应七与炔基锂反应R3B+LiCCR1CCR1R3BLiI2CCR1LiBRRRIIR2BRR1IRCCR1CCR1LiBRRRR2XR2BRR1R2H2O2NaOHHOAcRCHR1R2COHRR1R2R2BRR1CH2COYBrCH2COYH2O2NaOHRYOO八偶联反应八偶联反应RX:乙烯卤，芳卤，烯丙卤，苄卤乙烯卤，芳卤，烯丙卤，苄卤BSia2+RXRPd(PPh3)4NaOEt/EtOHPdL4RXRPdX L2R1ONaNaXRPdOR1 L2R