阿赫马托维奇反应

阿赫马托维奇反应是呋喃转变为二氢吡喃环的过程，1971年由小奥斯曼·阿赫马托维奇发现。^[1] 最初方法是用糠醇与溴在甲醇中反应，先得到2,5-二甲氧基-二氢糠醇，它用稀硫酸发生重排便得到一个二氢吡喃衍生物。该衍生物与原甲酸甲酯和三氟化硼反应上甲基保护基，接着用硼氢化钠还原酮基，可得另一二氢吡喃衍生物，这个产物可用作许多单糖的合成中间体。

这个反应用于天然产物desoxoprosophylline^[2]、核球壳菌素（Pyrenophorin）^[3]和包公藤甲素（Bao Gong Teng A）^[4] 和全合成中。

最近也用于定向多样性合成 ^[5] ^[6]

以及 enantiomeric scaffolding 中。^[7]^[8]

参见[编辑]

化学反应列表

参考资料[编辑]

^ Synthesis of methyl 2,3-dideoxy--alk-2-enopyranosides from furan compounds : A general approach to the total synthesis of monosaccharides Tetrahedron, Volume 27, Issue 10, 1971, Pages 1973-1996 O. Achmatowicz, P. Bukowski, B. Szechner, Z. Zwierzchowska and A. Zamojski doi:10.1016/S0040-4020(01)98229-8
^ Asymmetric total synthesis of (+)-desoxoprosophylline Tetrahedron Letters, Volume 39, Issue 50, 10 December 1998, Pages 9227-9228 Cui-Fen Yang, Yi-Ming Xu, Li-Xin Liao and Wei-Shan Zhou doi:10.1016/S0040-4039(98)02129-7
^ Efficient Conditions for Conversion of 2-Substituted Furans into 4-Oxygenated 2-Enoic Acids and Its Application to Synthesis of (+)-Aspicilin, (+)-Patulolide A, and (-)-Pyrenophorin Kobayashi, Y.; Nakano, M.; Kumar, G. B.; Kishihara, K. J. Org. Chem.; (Article); 1998; 63(21); 7505-7515. doi:10.1021/jo980942a
^ Organometallic Enantiomeric Scaffolding: Organometallic Chirons. Total Synthesis of (-)-Bao Gong Teng A by a Molybdenum-Mediated [5+2] Cycloaddition Yongqiang Zhang and Lanny S. Liebeskind J. Am. Chem. Soc. 2006; 128(2) pp 465 - 472; (Article) doi:10.1021/ja055623x
^ A Synthesis Strategy Yielding Skeletally Diverse Small Molecules Combinatorially Martin D. Burke, Eric M. Berger, and Stuart L. Schreiber J. Am. Chem. Soc. 126 (43), 14095 -14104, 2004. doi:10.1021/ja0457415
^ 试剂为：NBS、PPTS。另见固相合成。
^ Practical, Scalable, High-Throughput Approaches to 3-Pyranyl and 3-Pyridinyl Organometallic Enantiomeric Scaffolds Using the Achmatowicz Reaction Thomas C. Coombs, Maurice D. Lee, IV, Heilam Wong, Matthew Armstrong, Bo Cheng, Wenyong Chen, Alessandro F. Moretto, and Lanny S. Liebeskind J. Org. Chem. 73 (3), 882 -888, 2008. doi:10.1021/jo702006z
^ 过程为：氯甲酸苄酯为胺上Cbz保护基；mCPBA促进的阿赫马托维奇反应；与钼的配位。Cp=环戊二烯基。

[1] Synthesis of methyl 2,3-dideoxy--alk-2-enopyranosides from furan compounds : A general approach to the total synthesis of monosaccharides Tetrahedron, Volume 27, Issue 10, 1971, Pages 1973-1996 O. Achmatowicz, P. Bukowski, B. Szechner, Z. Zwierzchowska and A. Zamojski doi:10.1016/S0040-4020(01)98229-8

[2] Asymmetric total synthesis of (+)-desoxoprosophylline Tetrahedron Letters, Volume 39, Issue 50, 10 December 1998, Pages 9227-9228 Cui-Fen Yang, Yi-Ming Xu, Li-Xin Liao and Wei-Shan Zhou doi:10.1016/S0040-4039(98)02129-7

[3] Efficient Conditions for Conversion of 2-Substituted Furans into 4-Oxygenated 2-Enoic Acids and Its Application to Synthesis of (+)-Aspicilin, (+)-Patulolide A, and (-)-Pyrenophorin Kobayashi, Y.; Nakano, M.; Kumar, G. B.; Kishihara, K. J. Org. Chem.; (Article); 1998; 63(21); 7505-7515. doi:10.1021/jo980942a

[4] Organometallic Enantiomeric Scaffolding: Organometallic Chirons. Total Synthesis of (-)-Bao Gong Teng A by a Molybdenum-Mediated [5+2] Cycloaddition Yongqiang Zhang and Lanny S. Liebeskind J. Am. Chem. Soc. 2006; 128(2) pp 465 - 472; (Article) doi:10.1021/ja055623x

[5] A Synthesis Strategy Yielding Skeletally Diverse Small Molecules Combinatorially Martin D. Burke, Eric M. Berger, and Stuart L. Schreiber J. Am. Chem. Soc. 126 (43), 14095 -14104, 2004. doi:10.1021/ja0457415

[6] 试剂为：NBS、PPTS。另见固相合成。

[7] Practical, Scalable, High-Throughput Approaches to 3-Pyranyl and 3-Pyridinyl Organometallic Enantiomeric Scaffolds Using the Achmatowicz Reaction Thomas C. Coombs, Maurice D. Lee, IV, Heilam Wong, Matthew Armstrong, Bo Cheng, Wenyong Chen, Alessandro F. Moretto, and Lanny S. Liebeskind J. Org. Chem. 73 (3), 882 -888, 2008. doi:10.1021/jo702006z

[8] 过程为：氯甲酸苄酯为胺上Cbz保护基；mCPBA促进的阿赫马托维奇反应；与钼的配位。Cp=环戊二烯基。

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