Blum-Ittah 氮丙啶合成

Blum-Ittah氮丙啶合成反應（也叫Blum-Ittah-Shahak氮丙啶合成反應^[1]，或簡稱Blum氮丙啶合成反應）是一個有機化學中的人名反應，用於由環氧乙烷製備吖丙啶。 ^{[2][3][4][5][6][7][8][9]}

機理

環氧乙烷首先在疊氮根離子親核進攻下發生開環，轉化為2-疊氮醇。然後以類似於施陶丁格反應的方式被三烷基膦（如三苯基膦）還原，並釋放氮氣。然後膦亞胺中間體中的磷原子被羥基親核進攻，形成P-O鍵。由此構建了一個五元環中間體。質子轉移後，一對電子從氧原子轉移到磷原子上，磷氮鍵異裂，電子對再轉移到氮原子上。帶負電荷的氮原子進攻與氧原子相連的碳原子，形成了吖丙啶三元環。同時，該反應還生成了副產物三烷基氧磷。 ^{[2][3][4][7][9]}

應用

可以用Blum-Ittah吖丙啶合成反應合成α-甲基絲氨酸和6-氮雜環辛烷。^[5][8]

參考

1. 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. 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. 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. 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. 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.
6. 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. 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. 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. Li, Jie Jack. Name Reactions A Collection of Detailed Reaction Mechanisms. Springer. 2006: 63. ISBN 978-3-540-30030-4.