現(xiàn)代有機合成課件5-有機硼

1、第五章第五章 有機硼作中間體的合成反應有機硼作中間體的合成反應 B : 2s22p11. 極性極性： BHRCHCH2+BHRCHCH2HBRBH2R2BH R3B2. 烴基負離子源泉烴基負離子源泉 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鍵等鍵等 BR+:ABRB ARA一有機硼試劑的制備一有機硼試劑的制備1烴基硼烷的制備烴基硼烷的制備 3NaBH4+4BF3Et2OTHF2B2H6+3NaBF4+ 4Et2O2NaBH4+2HTHFB2H6+2Na2H2RCHCH2+ B2H6RCH2CH2BH2(1)(RCH2CH2)2BH+ RCHCH2(RC

2、H2CH2)3B(3)RCH2CH2BH2+ RCHCH2(RCH2CH2)2BH(2)反應速度：（反應速度：（1 1） （2 2） （3 3） 商業(yè)試劑：商業(yè)試劑： BH3.SMe2重要硼烷試劑重要硼烷試劑： CCH3CH3CHCH3+B2H6BHSecondary isoamyl boraneSia2BHH3CCHCH3CHCH32CCH3CH3CCH3CH3+B2H6HCCCH3CH3CH3CH3BH2thexyl boraneBH2+B2H6BH123456789HB9-borabicyclo3.3.1nonane9-BBNBH其它硼試劑其它硼試劑 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- -氫鍵的形成氫鍵的形成 1

6、還原反應還原反應在室溫下能使在室溫下能使 等還原等還原 C=O，COOR,COOH,CN作還原劑選擇性更好作還原劑選擇性更好 R2BH, RBH2可使可使 C=O C=O 還原，但還原，但COOR,COCl,COOH均不均不還原。還原。 BH2例例2. 硼氫化反應硼氫化反應CCHR2R1+B2H6CHCHR2RR1BOAcHHOAcCHCHR2RR1HRRCCR+Sia2BHCCRHRBSia2HOAcCCRHRH(順 式 ）Da-Ming Du, Tao Fang, Jiaxi Xu, and Shi-Wei Zhang Org. Lett. 2006, 8(7), 1327. 三碳氧鍵的形

7、成三碳氧鍵的形成 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四碳鹵鍵的形成四碳鹵鍵的形成RCHCH2(RCH2CH2)3BBr2NaOCH3NaI氯胺TRCH2CH2BrRCH2CH2

8、IBBrRRRBrBBrRRRBrOCH3B OCH3RR+R Br RCCHSia2BHCCRHHBSia2Br2反式加成CCRHHBSia2BrBrCCRHHBrBrBSia2CCRHHBr（E型）HOHCCRBrHHBrBSia2HOHCCRHBrH（Z型)五碳碳鍵的形成五碳碳鍵的形成 1烴化反應烴化反應 R3B+CHCBrOR2R1t-BuOKCHCOR2R1Rt-BuOHCH3+BHCH3BBrCH2COOEtt-BuOKCH3CH2CH2OOEt例例CHCBrOR2R1t-BuOKCCBrOR2R1R3BRBRCRR1BrCR2OBCRRRCR2R1OCHCRR1R2O+BRROB

9、ut-BuOH21，4加成反應加成反應CH2CHCOOR1R3B+(PhCOO)2RCH2CHCR1OBR2H2ORCH2CH2CORR3BO2RR+CH2CHCOR1RCH2CH CR1OR3BRCH2CH CR1OBR2+R例例 +BrMgBOO1.HOOH2.BH23. HOAc4. HCl/H2OOHHZ-型BrB3羰基化反應羰基化反應（1）合成叔醇）合成叔醇R3B+COR3CBOH2O2NaOHR3COH100125 0C常壓R3B+CORBRRCORBRRCOBORRRRRRBO例例BCB2H61. CO2. H2O2/NaOHOH（2）合成酮）合成酮R3B+CO +H2OBCOH

10、 OHRRRH2O2NaOHORRBCOH 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六與炔化物反應六與炔化物反應R

11、2BH+ HCCR1HR2BHR1I2NaOHBrCNRHHR1HHRR1BrCNHR2BHR1RBrBHR1HRNCRBrBHR1HRNCHHRR1HR2BHR1I2IHBHR1RRIRIBHR1HRIOHBIHR1RHRIRHHR1OHHBBr2 SMe2BBr2 SMe21/4 LiAlH4BHBr SMe2HCCC10H21-nHBHC10H21-nBrNaOCH3HBHC10H21-nOCH3I2/NaOCH3ArCO3HOHH七與炔基鋰反應七與炔基鋰反應R3B+LiCCR1CCR1R3BLiI2CCR1LiBRRRIIR2BRR1IRCCR1CCR1LiBRRRR2XR2BRR1R2H2O2NaOHHOAcRCHR1R2COHRR1R2R2BRR1CH2COYBrCH2COYH2O2NaOHRYOO八偶聯(lián)反應八偶聯(lián)反應RX:乙烯鹵，芳鹵，烯丙鹵，芐鹵乙烯鹵，芳鹵，烯丙鹵，芐鹵BSia2+RXRPd(PPh3)4NaOEt/EtOHPdL4RXRPdX L2R1ONaNaXRPdOR1 L2R