62965-35-9 N-Boc-L-叔亮氨酸
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分子式C11H21NO41.1±0.1 g/cm³比旋光度[α]20/D -4.5±1.5º (c=1%, AcOH) 沸点350.0±25.0 °C (760 mmHg) [13] Organic Letters, 2016, vol. 18, #18, p. 4518-4521[14] Bioorganic and Medicinal Chemistry, 2007, vol. 15, #2, p. 827-838[15] Journal of Medicinal Chemistry, 1998, vol. 41, #2, p. 199-223[16] Angewandte Chemie - International Edition, 2000, vol. 39, #15, p. 2752-2754[17] Bioorganic and medicinal chemistry letters, 2004, vol. 14, #1, p. 275-278[18] Chemistry - A European Journal, 2003, vol. 9, #17, p. 4031-4045[19] Chemistry - A European Journal, 2001, vol. 7, #5, p. 1014-1027[20] Journal of Medicinal Chemistry, 2008, vol. 51, #15, p. 4620-4631[21] Nature, 2009, vol. 461, #7266, p. 968-970[22] Chemistry - A European Journal, 2010, vol. 16, #44, p. 13068-13071[23] Bioorganic and Medicinal Chemistry Letters, 2011, vol. 21, #6, p. 1832-1837[24] Tetrahedron Asymmetry, 2011, vol. 22, #3, p. 300-308[25] Bioorganic and Medicinal Chemistry Letters, 2011, vol. 21, #8, p. 2425-2429[26] Chinese Chemical Letters, 2012, vol. 23, #3, p. 297-300[27] Chemical Communications, 2012, vol. 48, #42, p. 5193-5195[28] Chemistry - A European Journal, 2014, vol. 20, #21, p. 6526-6531[29] Journal of the American Chemical Society, 2014, vol. 136, #51, p. 17869-17881[30] Journal of Organic Chemistry, 2015, vol. 80, #15, p. 7770-7778[31] Tetrahedron, 2018, vol. 74, #52, p. 7485-7494路线2：L-叔亮氨酸与二碳酸二叔丁酯在1,4-二恶烷/水混合溶剂中反应
- 步骤：将三乙胺（890μL，6.40mmol）滴加到L-叔亮氨酸（300mg，2.29mmol）和二碳酸二叔丁酯（599mg，2.74mmol）的1,4-二恶烷/水1:1（8mL）溶液中，搅拌过夜；用石油醚（2×）萃取混合物，水相冷却至0℃，缓慢加入4M NaHSO₄·H₂O酸化至pH 3；酸化水相用EtOAc（3×）萃取，合并有机相用盐水（2×）洗涤，干燥、过滤、浓缩得无色粉末（522mg，99％），无需进一步纯化。
- 1H-NMR（300MHz，CD3OD）：δ0.99（s，9H），1.44（s，9H），3.96（s，1H）；
- 13C-NMR（75.5MHz，CD3OD）：δ27.1,28.7,34.9,68.0,80.5,157.8,174.7。
- 参考文献：
- [1] Patent: EP1881001, 2008, A1
- [2] Patent: EP1881002, 2008, A1
- 步骤：在四颈烧瓶中加入10.0g（1.0当量）N-Boc-叔丁基乙胺醇化合物、乙酸异丙酯100ml、溴化钠2.0eq、碳酸氢钠2.0eq、TMEPO 0.05eq，冷却至0-5℃；控制温度0-5℃滴加次氯酸钠1.2eq（约1.0-1.5h），保温2h后升温至20-25℃，保温1.0-2.0h；加入硫代硫酸钠固体0.6当量孵育0.5h；水层用20ml乙酸异丙酯萃取，分离相后向水层加20ml乙酸异丙酯，加柠檬酸调节pH至2-3，分离相后水层用20ml×2乙酸异丙酯萃取；合并有机层用50ml水洗涤，分离相后有机层用0.5g无水硫酸镁干燥0.5h，抽滤，滤液40-50℃蒸发至干，40-50℃保温下加5ml乙酸异丙酯，滴加25ml庚烷，缓慢冷却结晶，20-30℃保温0.5h，抽滤、洗涤得精制产物7.8g，收率73％，光学纯度100％。
- 参考文献：
- [1] Patent: CN107778192, 2018, A. Location in patent: Paragraph 0060-0062
