Blum-Ittah 氮丙啶合成
Blum-Ittah氮丙啶合成反应（也叫Blum-Ittah-Shahak氮丙啶合成反应[1]，或简称Blum氮丙啶合成反应）是一个有机化学中的人名反应，用于由环氧乙烷制备吖丙啶。 [2][3][4][5][6][7][8][9]
机理 编辑
环氧乙烷首先在叠氮根离子亲核进攻下发生开环，转化为2-叠氮醇。然后以类似于施陶丁格反应的方式被三烷基膦（如三苯基膦）还原，并释放氮气。然后膦亚胺中间体中的磷原子被羟基亲核进攻，形成P-O键。由此构建了一个五元环中间体。质子转移后，一对电子从氧原子转移到磷原子上，磷氮键异裂，电子对再转移到氮原子上。带负电荷的氮原子进攻与氧原子相连的碳原子，形成了吖丙啶三元环。同时，该反应还生成了副产物三烷基氧磷。 [2][3][4][7][9]
应用 编辑
参考 编辑
- ^ Hassner, Alfred; Namboothiri, Irishi. Organic Syntheses Based on Name Reactions: A Practical Guide to 750 Transformations. Elsevier. : 51. ISBN 978-0-08-096630-4.
- ^ 2.0 2.1 Ittah, Ytzhak; Sasson, Yoel; Shahak, Israel; Tsaroom, Shalom; Blum, Jochanan. A new aziridine synthesis from 2-azido alcohols and tertiary phosphines. Preparation of phenanthrene 9,10-imine. The Journal of Organic Chemistry. 1978-10-01, 43 (22): 4271–4273. doi:10.1021/jo00416a003.
- ^ 3.0 3.1 Ittah, Ytzhak; Shakah, Israel; Blum, Jochanan. Stable arene imines. The Journal of Organic Chemistry. 1978-02-01, 43 (3): 397–402. doi:10.1021/jo00397a004.
- ^ 4.0 4.1 Tanner, David; He, Hua Ming; Somfaib, Peter. Regioselective nucleophilic ring opening of 2,3-aziridino alcohols. Tetrahedron. 1992-05-18, 48 (29): 6069–6078. doi:10.1016/S0040-4020(01)89855-0.
- ^ 5.0 5.1 Wipf, Peter; Venkatraman, Srikanth; Miller, Chris P. A new synthesis of α-methylserine by nucleophilic ring-opening of N-sulfonyl aziridines. Tetrahedron Letters. 1995-05-22, 36 (21): 3639–3642. doi:10.1016/0040-4039(95)00621-I.
- ^ Fürmeier, Sandra; Metzger, Jürgen O. Fat-Derived Aziridines and Their N-Substituted Derivatives: Biologically Active Compounds Based on Renewable Raw Materials. European Journal of Organic Chemistry. 2003-01-23, 2003 (4): Pages 649–659. doi:10.1002/ejoc.200390105.
- ^ 7.0 7.1 Hili, Ryan; Yudin, Andrei K. Readily Available Unprotected Amino Aldehydes. Journal of the American Chemical Society. 2006-10-27, 128 (46): 14772–14773. doi:10.1021/ja065898s.
- ^ 8.0 8.1 Pulipaka, Aravinda B.; Bergmeier, Stephen C. A Synthesis of 6-Azabicyclo[3.2.1]octanes. The Role of N-Substitution. The Journal of Organic Chemistry. 2008-01-23, 73 (4): 1462–1467. doi:10.1021/jo702444c.
- ^ 9.0 9.1 Li, Jie Jack. Name Reactions A Collection of Detailed Reaction Mechanisms. Springer. 2006: 63. ISBN 978-3-540-30030-4.