Strecker反应
反应机理
经典的Strecker反应机理：
手性有机催化剂催化的反应：
反应实例
【Tetrahedron Lett. 1979, 20, 4663–4666】
【J. Labelled. Compd. Radiopharm. 2000, 43, 891–898】
【J. Org. Chem. 2001, 66, 7355-7364】
【J. Org. Chem. 2002, 67, 7802-7806】
【Chem. Eur. J. 2002, 8, 439-450】
【Tetrahedron: Asymmetry 2005, 16, 2613–2523】
【Bioorg. Med. Chem. Lett. 2006, 16, 3859–3863】
【Tetrahedron: Asymmetry 2008, 19, 2804-2815】
不对称Strecker反应合成硝酮。
【Org. Lett. 2013, 15, 2422–2425】
Adolph Strecker在160多年前发现了此反应。在它的论文中写道：“反应制备的大块甘氨酸晶体像珍珠母一样闪亮，坚硬，嚼起来嘎嘣脆。” P.S. \(^o^)/对自己的纯化水平极度自信啊，残留一点氰化钠可就挂了。
相关文献
1. Strecker, A. Ann. 1850, 75, 27-45.
2. Harusawa, S.; Hamada, Y.; Shioiri, T. Tetrahedron Lett. 1979, 20, 4663–4666.
3. Burgos, A.; Herbert, J. M.; Simpson, I. J. Labelled. Compd. Radiopharm. 2000, 43, 891–898.
4. Ishitani, H.; Komiyama, S.; Hasegawa, Y.; Kobayashi, S. J. Am. Chem. Soc. 2000, 122, 762–766.
5. Yet, L. Recent Developments in Catalytic Asymmetric Strecker-Type Reactions, in Organic Synthesis Highlights V, Schmalz, H.-G.; Wirth, T. eds.; Wiley-VCH: Weinheim, Germany, 2003, pp 187-193. (Review).
6. Meyer, U.; Breitling, E.; Bisel, P.; Frahm, A. W. Tetrahedron: Asymmetry 2004, 15, 2029–2037.
7. Huang, J.; Corey, E. J. Org. Lett. 2004, 6, 5027–5029.
8. Cativiela, C.; Lasa, M.; Lopez, P. Tetrahedron: Asymmetry 2005, 16, 2613–2523.
9. Wrobleski, M. L.; Reichard, G. A.; Paliwal, S.; Shah, S.; Tsui, H.-C.; Duffy, R. A.; Lachowicz, J. E.; Morgan, C. A.; Varty, G. B.; Shih, N.-Y. Bioorg. Med. Chem. Lett. 2006, 16, 3859–3863.
10. Galatsis, P. Strecker Amino Acid Synthesis. In Name Reactions for Functional Group Transformations; Li, J. J., Ed.; Wiley: Hoboken, NJ, 2007, pp 477-499. (Review).
11. Belokon, Y. N.; Hunt, J.; North, M. Tetrahedron: Asymmetry 2008, 19, 2804-2815.
12. Sakai, T.; Soeta, T.; Endo, K.; Fujinami, S.; Ukaji, Y. Org. Lett. 2013, 15, 2422–2425.
不对称合成改进法：
(a) catalytic asymmetric Strecker reaction (e.g., aldehyde+amine+HCN+methylimidazole binaphthyl zirconium, aldehyde+ amine + TMSCN + praseodymium trifluoromethylsulfonate);
(b) the addition of cyanide or its equivalent to an imine in the presence of a chiral catalyst [e.g., TMSCN +Ti(O-i-Pr)4 + chiral Schiff base, TMSCN + chiral trihydroxyl tetrahydropyran, HCN+ peptide with chiral cyclohexadiamine component, Vall´ee’s heterobimetallic catalyst, HCN + (R)-proline derived DHQD-PHAL catalyst, HCN + chiral bicyclic guanidine, HCN + chiral piperazinedione]；
(c) addition of cyanide to a sulfinimine [KCN with a chiral quaternary ammonium salt with tetranaphthyl backbone as the phase-transfer catalyst, Et2AlCN to chiral sulfinimine, ethyl aluminum cyano alkoxide (EtAl(OR)CN)+ chiral sulfinimine, TMSCN + CsF + chiral sulfinimine (good for both aliphatic andaromatic aldehyde)]；
(d) nucleophilic addition of a carbon nucleophile to an imine of
α-ketoacid or ester in the presence of a chiral catalyst (e.g., addition of enolate in the presence of l-proline)；
(e) internal rearrangement of a chiral allyl trichloroimidate;
(f ) kinetic resolution of a diasteromeric mixture (including the crystallization-induced asymmetric transformation of amino acid using (R)-phenylglycine amide as the chiral auxiliary and cinchona alkaloid catalyzed kinetic resolution of urethane protected α-amino acid).
【Comprehensive Organic Name Reactions and Reagents, by Zerong Wang，P 2712】
参考资料
一、Name Reactions （A Collection of Detailed Reaction Mechanisms）, Jie Jack Li, Strecker amino acid synthesis，page 591-592.
二、Strategic Applications of Named Reactions in Organic Synthesis, László Kürti and Barbara Czakó, Streckerreaction, page 446-447.
三、Comprehensive Organic Name Reactions and Reagents, by Zerong Wang，P 2712.