相关反应

Fleming-Tamao氧化

马尔科夫尼科夫法则

醇的合成

硼烷的合成

Related Reactions

Fleming-Tamao Oxidation

Markovnikov's Rule

Synthesis of Alcohols

Synthesis of Boranes

Brown Hydroboration   布朗硼氢化反应

氢硼烷与烯烃的合成加成具有可预测的选择性，其中硼优先添加到阻碍最小的碳中。如果使用立体要求的硼烷，这种选择性会增强。

将氢化硼化与新形成的硼烷的后续氧化反应耦合，得到抗马尔可夫尼科夫醇。氢化硼化/氧化序列是一种有效的区域和立体选择性合成醇的方法。

硼烷产品也可用作其他反应的起始材料，如铃木联轴器（见最新文献）。

布朗氢硼化反应机理

首次加入硼烷的选择性相对较低：

随着立体体积的增加，随后的添加更具选择性，最终反马尔可夫尼科夫选择性占主导地位：

用过氧化氢氧化会导致醇类：

空间要求高的硼烷提供了增强的选择性。空间要求高的硼烷(9-BBN)的一个例子是通过向1,5-环辛二烯中双加硼烷而生成的：

硼烷试剂的反应性和选择性可以通过使用硼烷-路易斯碱配合物来改变。

Recent Literature

Hydroboration. 97. Synthesis of New Exceptional Chloroborane-Lewis Base Adducts for Hydroboration. Dioxane-Monochloroborane as a Superior Reagent for the Selective Hydroboration of Terminal Alkenes
J. V. B. Kanth, H. C. Brown, J. Org. Chem, 2001, 66, 5359-5365.

Hydroboration with Pyridine Borane at Room Temperature
J. M. Clay, E. Vedejs, J. Am. Chem. Soc., 2005, 127, 5766-5767.

Hydroboration with Pyridine Borane at Room Temperature
J. M. Clay, E. Vedejs, J. Am. Chem. Soc., 2005, 127, 5766-5767.

Sodium perborate: a mild and convenient reagent for efficiently oxidizing organoboranes
G. W. Kabalka, T. M. Shoup, N. M. Goudgaon, J. Org. Chem., 1989, 5930-5933.

Dod-S-Me and Methyl 6-Morpholinohexyl Sulfide (MMS) as New Odorless Borane Carriers
P. K. Patra, K. Nishide, K. Fuji, M. Node, Synthesis, 2004, 1003-1006.

Synthesis of Tertiary Alkyl Amines from Terminal Alkenes: Copper-Catalyzed Amination of Alkyl Boranes
R. P. Rucker, A. M. Whittaker, H. Dang, G. Lalic, J. Am. Chem. Soc., 2012, 134, 6571-6574.

Highly Selective Bis(imino)pyridine Iron-Catalyzed Alkene Hydroboration
J. V. Obligacion, P. J. Chirik, Org. Lett., 2013, 15, 2680-2683.

Borane-Catalysed Hydroboration of Alkynes and Alkenes
N. W. J. Ang, C. S. Buettner, S. Docherty, A. Bismuto, J. R. Carney, J. H. Docherty, M. J. Cowley, S. P. Thomas, Synthesis, 2018, 50, 803-808.

Preparation of (E)-1-Alkenylboronic Acid Pinacol Esters via Transfer of Alkenyl Group from Boron to Boron
K. Shirakawa, A. Arase, M. Hoshi, Synthesis, 2004, 1814-1820.

Highly Stereoselective Synthesis of cis-Alkenyl Pinacolboronates and Potassium cis-Alkenyltrifluoroborates via a Hydroboration/Protodeboronation Approach
G. A. Molander, N. M. Ellis, J. Org. Chem., 2008, 73, 6841-6844.

Iron-Catalyzed 1,4-Hydroboration of 1,3-Dienes
J. Y. Wu, B. Moreau, T. Ritter, J. Am. Chem. Soc., 2009, 131, 12915-12917.

Nickel-Catalyzed 1,4-Addition of Trialkylboranes to α,β-Unsaturated Esters: Dramatic Enhancement by Addition of Methanol
K. Hirano, H. Yorimitsu, K. Oshima, Org. Lett., 2007, 9, 1541-1544.

Regioselective Semihydrogenation of Dienes
T. J. A. Graham, T. H. Poole, C. N. Reese, B. C. Goess, J. Org. Chem., 2011, 76, 4132-4138.

Regioselective and Stereoselective Entry to β,β-Disubstituted Vinyl Ethers via the Sequential Hydroboration/Suzuki-Miyaura Coupling of Ynol Ethers
W. Cui, M. Mao, Z. He, G. Zhu, J. Org. Chem., 2013, 78, 9815-9821.

Concise Formation of 4-Benzyl Piperidines and Related Derivatives Using a Suzuki Protocol
S. Vice, T. Bara, A. Bauer, C. A. Evans, J. Fort, H. Josien, S. McCombie, M. Miller, D. Nazzareno, A. Palani, J. Tagat,  J. Org. Chem, 2001, 66, 2487-2492.

An Exceptional Hydroboration of Substituted Fluoroolefins Providing Tertiary Alcohols
P. V. Ramachandran, M. P. Jennings, Org. Lett., 2001, 3, 3789-3790.