甲硫醚硼烷

甲硫醚硼烷
别名	BMS, Borane-dimethyl sulfide
识别
CAS号	13292-87-0
PubChem	12423031
SMILES	[BH3-][S+](C)C;
性质
化学式	(CH3)2SBH3
摩尔质量	75.96 g·mol⁻¹
外观	无色液体
密度	0.801 g/mL
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

甲硫醚硼烷（BMS）是络合硼烷试剂，用于硼氢化反应和还原反应，比四氢呋喃硼烷等硼烷试剂稳定和溶解度高，^[1]市售浓度比四氢呋喃硼烷（10摩）高得多，亦不需可能会导致副反应的硼氢化钠作稳定剂；^[2]相反，四氢呋喃硼烷需要硼氢化钠来抑制THF还原四氢呋喃硼烷硼烷为硼酸三丁酯。^[2]甲硫醚硼烷可溶于多数非质子溶剂。

合成和结构

虽然通常不会在实验室合成，但可以甲硫醚吸收乙硼烷制成：^[3]

B₂H₆＋2SMe₂　→　2Me₂SBH₃

它可以灯泡到灯泡真空转移（bulb to bulb vacuum transfer）来净化。虽然其结构尚未以晶体学确定，但以X光晶体学检验甲硫醚五氟苯硼烷（Me₂SBH₂C₆F₅），^[4]硼中心构型为四面体。

反应

硼氢化反应

甲硫醚硼烷易用，常用于硼氢化反应，反应时就地解离，释出乙硼烷，乙硼烷迅速加入不饱和键。所得有机硼烷化合物是有机合成的有用中间体。硼烷以反马氏方式加到烯烃，并将炔烃转为顺烯。

还原

甲硫醚硼烷可还原多种官能团，醛、酮、环氧化物、酯和羧酸还原为相应的醇；内酯还原为二醇；腈还原为胺，但不会还原酰氯和硝基。

甲硫醚硼烷是高利－伊津野还原常用的本体还原剂。甲硫醚配体抑制硼烷的活性。以计量还原剂的手性恶唑硼烷催化剂的氮激活允许不对称控制试剂。（按：Activation by the nitrogen of the chiral oxazoborolidine catalyst of the stoichiometric reducing agent allows for asymmetric control of the reagent.这句原文有点怪）甲硫醚硼烷的对映体选择度通常不比四氢呋喃硼烷显著，但在有水有氧环境较稳定，是首选还原剂。^[5]

安全

甲硫醚硼烷可燃，与水反应产生易燃气体，气味难闻。^[6]

参考资料

^ Hutchins, Robert O.; Cistone, Frank. Utility and Applications of Borane Dimethylsulfide in Organic Synthesis. A Review. Organic Preparations and Procedures International. 1981, 13 (3–4): 225. doi:10.1080/00304948109356130.
^ ^2.0 ^2.1 Kollonitisch, J. Reductive Ring Cleavage of Tetrahydrofurans by Diborane. J. Am. Chem. Soc. 1961, 83 (6): 1515. doi:10.1021/ja01467a056.
^ Braun, L. M.; Braun, R. A.; Crissman, R.; Opperman, M.; Adams, R. M. Dimethyl Sulfide-Borane. A Convenient Hydroborating Reagent. J. Org. Chem. 1971, 36 (16): 2388–2389. doi:10.1021/jo00815a047.
^ Fuller, Anna-Marie; Hughes, David L.; Lancaster, Simon J.; White, Callum M. Synthesis and Structure of the Dimethyl Sulfide Adducts of Mono- and Bis(pentafluorophenyl)borane. Organometallics. 2010, 29 (9): 2194. doi:10.1021/om100152v.
^ Corey, E.J.; Helal, C. J. Reduction of Carbonyl Compounds with Chiral Oxazoborolidine Catalysts: A New Paradigm for Enantioselective Catalysis and a Powerful New Synthetic Method. Angew. Chem. Int. Ed. 1998, 37 (15): 1986–2012. doi:10.1002/(SICI)1521-3773(19980817)37:15<1986::AID-ANIE1986>3.0.CO;2-Z.
^ Sigma-Aldrich Material Safety Data Sheet. www.sigmaaldrich.com/. [29 November 2014]. （原始内容存档于2018-01-21）.

[1] Hutchins, Robert O.; Cistone, Frank. Utility and Applications of Borane Dimethylsulfide in Organic Synthesis. A Review. Organic Preparations and Procedures International. 1981, 13 (3–4): 225. doi:10.1080/00304948109356130.

[Kollonitisch_1961-2] 2.0 ^2.1 Kollonitisch, J. Reductive Ring Cleavage of Tetrahydrofurans by Diborane. J. Am. Chem. Soc. 1961, 83 (6): 1515. doi:10.1021/ja01467a056.

[3] Braun, L. M.; Braun, R. A.; Crissman, R.; Opperman, M.; Adams, R. M. Dimethyl Sulfide-Borane. A Convenient Hydroborating Reagent. J. Org. Chem. 1971, 36 (16): 2388–2389. doi:10.1021/jo00815a047.

[4] Fuller, Anna-Marie; Hughes, David L.; Lancaster, Simon J.; White, Callum M. Synthesis and Structure of the Dimethyl Sulfide Adducts of Mono- and Bis(pentafluorophenyl)borane. Organometallics. 2010, 29 (9): 2194. doi:10.1021/om100152v.

[5] Corey, E.J.; Helal, C. J. Reduction of Carbonyl Compounds with Chiral Oxazoborolidine Catalysts: A New Paradigm for Enantioselective Catalysis and a Powerful New Synthetic Method. Angew. Chem. Int. Ed. 1998, 37 (15): 1986–2012. doi:10.1002/(SICI)1521-3773(19980817)37:15<1986::AID-ANIE1986>3.0.CO;2-Z.

[6] Sigma-Aldrich Material Safety Data Sheet. www.sigmaaldrich.com/. [29 November 2014]. （原始内容存档于2018-01-21）.

[1]

[2]

[3]

[4]

[5]

[6]