三(2,2,2-三氟乙氧基)硼

三(2,2,2-三氟乙氧基)硼
别名	Sheppard酰胺化试剂; Sheppard试剂; 硼酸三(2,2,2,-三氟乙酯)
识别
CAS号	659-18-7
PubChem	3599767
SMILES	FC(F)(F)COB(OCC(F)(F)F)OCC(F)(F)F;
性质
化学式	B(OCH2CF3)3
摩尔质量	307.91 g·mol⁻¹
外观	无色液体
密度	1.430 g/mL
沸点	94.3 °C（367 K）
危险性
H-术语	H226
主要危害	可燃液体和气体
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

三(2,2,2-三氟乙氧基)硼，又称Sheppard酰胺化试剂，^[1]化学式 B(OCH₂CF₃)₃。这种硼酸酯可用于有机合成。

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制备

三(2,2,2-三氟乙氧基)硼可以由三氟乙醇和三氯化硼、二甲硫醚硼烷（英语：borane dimethylsulfide）、三溴化硼或三氧化二硼反应而成。其中，三氧化二硼成本低且易于处理，因此更便于大规模制备。^[2]

CF₃CH₂OH + B₂O₃ → B(OCH₂CF₃)₃

产物可以通过蒸馏提纯。

应用

三(2,2,2-三氟乙氧基)硼大多用于缩合反应。它可以反应羧酸和胺，形成酰胺；^[2]^[3]^[4]^[5]也可以把胺或酰胺与羰基化合物反应，形成亚胺^[6]。

它还用于将未保护的氨基酸与胺偶联。^[4]^[7]

三(2,2,2-三氟乙氧基)硼是一种强路易斯酸（AN = 66，Gutmann-Beckett法（英语：Gutmann-Beckett method））。^[8]

参考资料

[1]
Tris(2,2,2-trifluoroethyl) borate 97% | Sigma-Aldrich. www.sigmaaldrich.com. [2016-09-21].
[2]
Lanigan, Rachel M.; Starkov, Pavel; Sheppard, Tom D. Direct Synthesis of Amides from Carboxylic Acids and Amines Using B(OCH2CF3)3. The Journal of Organic Chemistry. 2013-05-03, 78 (9): 4512–4523. ISSN 0022-3263. PMC 3671500 . PMID 23586467. doi:10.1021/jo400509n.
[3]
Karaluka, Valerija; Lanigan, Rachel M.; Murray, Paul M.; Badland, Matthew; Sheppard, Tom D. B(OCH2CF3)3-mediated direct amidation of pharmaceutically relevant building blocks in cyclopentyl methyl ether (PDF). Organic & Biomolecular Chemistry. 2015-11-03, 13 (44): 10888–10894 [2021-07-31]. ISSN 1477-0539. PMID 26366853. doi:10.1039/C5OB01801C . （原始内容存档 (PDF)于2018-07-23）（英语）.
[4]
Lanigan, Rachel M.; Karaluka, Valerija; Sabatini, Marco T.; Starkov, Pavel; Badland, Matthew; Boulton, Lee; Sheppard, Tom D. Direct amidation of unprotected amino acids using B(OCH2CF3)3. Chemical Communications. 2016-07-07, 52 (57): 8846–8849. ISSN 1364-548X. PMID 27346362. doi:10.1039/C6CC05147B  （英语）.
[5]
Sabatini, Marco T.; Boulton, Lee T.; Sheppard, Tom D. Borate esters: Simple catalysts for the sustainable synthesis of complex amides. Science Advances. 2017-09-01, 3 (9): e1701028. Bibcode:2017SciA....3E1028S. ISSN 2375-2548. PMC 5609808 . PMID 28948222. doi:10.1126/sciadv.1701028 （英语）.
[6]
Reeves, Jonathan T.; Visco, Michael D.; Marsini, Maurice A.; Grinberg, Nelu; Busacca, Carl A.; Mattson, Anita E.; Senanayake, Chris H. A General Method for Imine Formation Using B(OCH2CF3)3. Organic Letters. 2015-05-15, 17 (10): 2442–2445. ISSN 1523-7060. PMID 25906082. doi:10.1021/acs.orglett.5b00949.
[7]
Sabatini, Marco; Karaluka, Valerija; Lanigan, Rachel; Boulton, Lee; Badland, Matthew; Sheppard, Tom David. Protecting-group-free amidation of amino acids using Lewis acid catalysts. Chemistry - A European Journal. 2018, 24 (27): 7033–7043. ISSN 1521-3765. PMC 5969221 . PMID 29505683. doi:10.1002/chem.201800372 （英语）.
[8]
Beckett, Michael A; Rugen-Hankey Martin P; Strickland, Gary C; Varma, K. Sukumar, Lewis acidity in haloalkyl orthoborate and metaborate esters, (2001) Phosphorus, Sulfur, and Silicon, 168, 437-440.

扩展阅读

Related reagent tris(2,2,2-trinitroethyl)borate: Klapötke, Thomas M.; Krumm, Burkhard; Rusan, Magdalena; Sabatini, Jesse J. Improved green-light-emitting pyrotechnic formulations based on tris(2,2,2-trinitroethyl)borate and boron carbide. Chem. Commun. 2014, 50 (67): 9581–9583. PMID 25012058. doi:10.1039/c4cc04616a .

[1] [1]
Tris(2,2,2-trifluoroethyl) borate 97% | Sigma-Aldrich. www.sigmaaldrich.com. [2016-09-21].

[:0-2] [2]
Lanigan, Rachel M.; Starkov, Pavel; Sheppard, Tom D. Direct Synthesis of Amides from Carboxylic Acids and Amines Using B(OCH2CF3)3. The Journal of Organic Chemistry. 2013-05-03, 78 (9): 4512–4523. ISSN 0022-3263. PMC 3671500 . PMID 23586467. doi:10.1021/jo400509n.

[3] [3]
Karaluka, Valerija; Lanigan, Rachel M.; Murray, Paul M.; Badland, Matthew; Sheppard, Tom D. B(OCH2CF3)3-mediated direct amidation of pharmaceutically relevant building blocks in cyclopentyl methyl ether (PDF). Organic & Biomolecular Chemistry. 2015-11-03, 13 (44): 10888–10894 [2021-07-31]. ISSN 1477-0539. PMID 26366853. doi:10.1039/C5OB01801C . （原始内容存档 (PDF)于2018-07-23）（英语）.

[:1-4] [4]
Lanigan, Rachel M.; Karaluka, Valerija; Sabatini, Marco T.; Starkov, Pavel; Badland, Matthew; Boulton, Lee; Sheppard, Tom D. Direct amidation of unprotected amino acids using B(OCH2CF3)3. Chemical Communications. 2016-07-07, 52 (57): 8846–8849. ISSN 1364-548X. PMID 27346362. doi:10.1039/C6CC05147B  （英语）.

[5] [5]
Sabatini, Marco T.; Boulton, Lee T.; Sheppard, Tom D. Borate esters: Simple catalysts for the sustainable synthesis of complex amides. Science Advances. 2017-09-01, 3 (9): e1701028. Bibcode:2017SciA....3E1028S. ISSN 2375-2548. PMC 5609808 . PMID 28948222. doi:10.1126/sciadv.1701028 （英语）.

[6] [6]
Reeves, Jonathan T.; Visco, Michael D.; Marsini, Maurice A.; Grinberg, Nelu; Busacca, Carl A.; Mattson, Anita E.; Senanayake, Chris H. A General Method for Imine Formation Using B(OCH2CF3)3. Organic Letters. 2015-05-15, 17 (10): 2442–2445. ISSN 1523-7060. PMID 25906082. doi:10.1021/acs.orglett.5b00949.

[7] [7]
Sabatini, Marco; Karaluka, Valerija; Lanigan, Rachel; Boulton, Lee; Badland, Matthew; Sheppard, Tom David. Protecting-group-free amidation of amino acids using Lewis acid catalysts. Chemistry - A European Journal. 2018, 24 (27): 7033–7043. ISSN 1521-3765. PMC 5969221 . PMID 29505683. doi:10.1002/chem.201800372 （英语）.

[8] [8]
Beckett, Michael A; Rugen-Hankey Martin P; Strickland, Gary C; Varma, K. Sukumar, Lewis acidity in haloalkyl orthoborate and metaborate esters, (2001) Phosphorus, Sulfur, and Silicon, 168, 437-440.

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