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Strychnine total synthesis in chemistry describes the total synthesis of the complex biomolecule strychnine. The first reported method by the group of Robert Burns Woodward in 1954 is considered a classic in this research field.〔Nicolaou, K. C.; Sorensen, E. J. (1996). Classics in Total Synthesis: Targets, Strategies, Methods. Wiley. ISBN 978-3-527-29231-8.〕〔''The Art and Science of Total Synthesis at the Dawn of the Twenty-First Century'' Angewandte Chemie International Edition Volume 39, Issue 1, Date: January 3, 2000, Pages: 44-122 K. C. Nicolaou, Dionisios Vourloumis, Nicolas Winssinger, Phil S. Baran〕〔''Synthesis of Strychnine'' Josep Bonjoch and Daniel Sole Chem. Rev. 2000, 100, 3455-3482 〕 〔 ''Reaction Schemes Visualized in Network Form: The Syntheses of Strychnine as an Example'' John R. Proudfoot Journal of Chemical Information and Modeling Article ASAP 〕 At the time it formed the natural conclusion to an elaborate process of molecular structure elucidation that started with the isolation of strychnine from the beans of ''Strychnos ignatii'' by Pierre Joseph Pelletier and Joseph Bienaimé Caventou in 1818.〔Pelletier and Caventou (1818) ("Note sur un nouvel alkalai" ) (Note on a new alkali), ''Annales de Chimie et de Physique'', vol. 8, pages 323-324. See also: Pelletier and Caventou (1819) ("Mémoire sur un nouvel alcali vegetal (la strychnine) trouvé dans la feve de Saint-Ignace, la noix vomique, etc." ) (Memoir on a new vegetable alkali (strychnine) found in the St. Ignatius bean, the nux vomica, etc), ''Annales de Chimie et de Physique'', vol. 10, pages 142-176.〕 Major contributors to the entire effort were Sir Robert Robinson with over 250 publications and Hermann Leuchs with another 125 papers in a time span of 40 years. Robinson was awarded the Nobel Prize in Chemistry in 1947 for his work on alkaloids, strychnine included. The process of chemical identification was completed with publications in 1946 by Robinson 〔''The constitution of strychnine'' R. Robinson Experientia Issue Volume 2, Number 1 / January, 1946 〕〔''Strychnine and brucine. Part XLII. Constitution of the neo-series of bases and their oxidation products'' L. H. Briggs, H. T. Openshaw and Sir Robert Robinson, J. Chem. Soc., 1946, 903 〕〔''Constitution of Strychnine and the Biogenetic Relationship of Strychnine and Quinine'' H. T. OPENSHAW & R. ROBINSON nature 157, 438-438 (6 April 1946) | 〕 and later confirmed by Woodward in 1947.〔THE STRUCTURE OF STRYCHNINE R. B. Woodward, Warren J. Brehm, A. L. Nelson J. Am. Chem. Soc., 1947, 69 (9), p 2250 〕 X-ray structures establishing the absolute configuration became available between 1947 and 1951 with publications from J. M. Bijvoet 〔Bijvoet , Schoone and Bokhoven , Kon. Ned. Akad. Wet., 50, No 8, 51, No. 8, 52, No. 2 (1947–49)〕〔'' The Fourier synthesis of the crystal structure of strychnine sulphate pentahydrate'' C. Bokhoven, J. C. Schoone and J. M. Bijvoet Acta Cryst. (1951). 4, 275-280 〕 and J.H. Robertson 〔''Crystal Structure of Strychnine Hydrobromide'' J. H. ROBERTSON & C. A. BEEVERS Nature 165, 690 - 691 1950 〕 .〔''The crystal structure of strychnine hydrogen bromide'' J. H. Robertson and C. A. Beevers Acta Cryst. (1951). 4, 270-275 〕 Woodward published a very brief account on the strychnine synthesis in 1954 (just 3 pages) 〔THE TOTAL SYNTHESIS OF STRYCHNINE R. B. Woodward, Michael P. Cava, W. D. Ollis, A. Hunger, H. U. Daeniker, K. Schenker J. Am. Chem. Soc., 1954, 76 (18), pp 4749–4751 〕 and a lengthy one (42 pages) in 1963.〔''The total synthesis of strychnine'' Tetrahedron, Volume 19, Issue 2, 1963, Pages 247-288 R. B. Woodward, M. P. Cava, W. D. Ollis, A. Hunger, H. U. Daeniker, K. Schenker〕 Many more methods exist and reported by the research groups of Magnus,〔''Synthesis of strychnine via the Wieland-Gumlich aldehyde'' Philip Magnus, Melvyn Giles, Roger Bonnert, Chung S. Kim, Leslie McQuire, Andrew Merritt, Nigel Vicker J. Am. Chem. Soc., 1992, 114 (11), pp 4403–4405 〕 Overman,〔''Synthesis applications of cationic aza-Cope rearrangements. 26. Enantioselective total synthesis of (−)-strychnine'' Steven D. Knight, Larry E. Overman, Garry Pairaudeau J. Am. Chem. Soc., 1993, 115 (20), pp 9293–9294 〕 Kuehne,〔''Total synthesis of strychnan and aspidospermatan alkaloids. 3. The total synthesis of (+-)-strychnine'' Martin E. Kuehne, Feng Xu J. Org. Chem., 1993, 58 (26), pp 7490–7497 〕〔''Syntheses of Strychnan- and Aspidospermatan-Type Alkaloids. 10. An Enantioselective Synthesis of (−)-Strychnine through the Wieland−Gumlich Aldehyde'' Martin E. Kuehne and Feng Xu J. Org. Chem., 1998, 63 (25), pp 9427–9433 〕 Rawal,〔''A Short, Stereocontrolled Synthesis of Strychnine'' Viresh H. Rawal, Seiji Iwasa J. Org. Chem., 1994, 59 (10), pp 2685–2686 〕 Bosch,〔''Total Synthesis of (−)-Strychnine via the Wieland-Gumlich Aldehyde'' Angewandte Chemie International Edition Volume 38, Issue 3, Date: February 1, 1999, Pages: 395-397 Daniel Solé, Josep Bonjoch, Silvina García-Rubio, Emma Peidró, Joan Bosch〕〔''Enantioselective Total Synthesis of Wieland-Gumlich Aldehyde and (−)-Strychnine '' Daniel Solé, Josep Bonjoch, Silvina García-Rubio, Emma Peidró, Joan Bosch Chemistry - A European Journal Volume 6 Issue 4, Pages 655 - 665 Published Online: 22 Feb 2000 〕 Vollhardt,〔''The Formal Total Synthesis of (±)-Strychnine via a Cobalt-Mediated (+ 2 + 2 )Cycloaddition'' Michael J. Eichberg, Rosa L. Dorta, Kai Lamottke, and K. Peter C. Vollhardt Org. Lett., 2000, 2 (16), pp 2479–2481 〕〔''Approaches to the Synthesis of (±)-Strychnine via the Cobalt-Mediated (+ 2 + 2 ) Cycloaddition: Rapid Assembly of a Classic Framework'' Michael J. Eichberg, Rosa L. Dorta, Douglas B. Grotjahn, Kai Lamottke, Martin Schmidt, and K. Peter C. Vollhardt J. Am. Chem. Soc., 2001, 123 (38), pp 9324–9337 〕 Mori,〔''Total Synthesis of (−)-Strychnine'' Angewandte Chemie International Edition Volume 41, Issue 11, Date: June 3, 2002, Pages: 1934-1936 Masato Nakanishi, Miwako Mori 〕〔''A Novel and General Synthetic Pathway to Strychnos Indole Alkaloids: Total Syntheses of (−)-Tubifoline, (−)-Dehydrotubifoline, and (−)-Strychnine Using Palladium-Catalyzed Asymmetric Allylic Substitution'' Miwako Mori, Masato Nakanishi, Daisuke Kajishima, and Yoshihiro Sato J. Am. Chem. Soc., 2003, 125 (32), pp 9801–9807 〕 Shibasaki,〔''Enantioselective Total Synthesis of (−)-Strychnine Using the Catalytic Asymmetric Michael Reaction and Tandem Cyclization'' Takashi Ohshima, Youjun Xu, Ryo Takita, Satoshi Shimizu, Dafang Zhong, and Masakatsu Shibasaki J. Am. Chem. Soc., 2002, 124 (49), pp 14546–14547 〕 Li,〔''A Concise Formal Total Synthesis of (±)-Strychnine by Using a Transannular Inverse-Electron-Demand Diels-Alder Reaction of a ()(1,3)Indolo()(3,6)pyridazinophane'' Angewandte Chemie International Edition Volume 41, Issue 17, Date: September 2, 2002, Pages: 3261-3262 Graham J. Bodwell, Jiang Li 〕 Fukuyama 〔''Total synthesis of (−)-strychnine'' Kaburagi Y, Tokuyama H, Fukuyama T J. Am. Chem. Soc. 2004 Volume: 126 Issue: 33 Pages: 10246-10247 〕 Vanderwal and MacMillan.〔''Collective synthesis of natural products by means of organocascade catalysis'' Spencer B. Jones, Bryon Simmons, Anthony Mastracchio, David W. C. MacMillan Nature 475, 183–188 〕 Synthetic (+)-strychnine is also known.〔''Asymmetric Total Syntheses of (−)- and (+)-Strychnine and the Wieland-Gumlich Aldehyde'' Steven D. Knight, Larry E. Overman, Garry Pairaudeau J. Am. Chem. Soc., 1995, 117 (21), pp 5776–5788 〕〔Not counted:an unpublished method by Gilbert Stork, Lecture at the Ischia School of Organic Chemistry, Ischia Porb, Italy, September 21,1992.〕 Racemic synthesises were published by Padwa in 2007 〔''Total Synthesis of (±)-Strychnine via a (+ 2 )-Cycloaddition/Rearrangement Cascade'' Hongjun Zhang, Jutatip Boonsombat, and Albert Padwa Org. Lett., 2007, 9 (2), pp 279–282 〕 and in 2010 by Andrade 〔''Concise Total Syntheses of (±)-Strychnine and (±)-Akuammicine'' Gopal Sirasani, Tapas Paul, William Dougherty Jr., Scott Kassel, Rodrigo B. Andrade The Journal of Organic Chemistry 2010 75 (10), 3529-3532 〕 and by Reissig.〔Beemelmanns, C. and Reissig, H.-U. , ''A Short Formal Total Synthesis of Strychnine with a Samarium Diiodide Induced Cascade Reaction as the Key Step''. Angewandte Chemie International Edition, 2010, 49 (43), pp 8021–8025〕 In his 1963 publication Woodward quoted Sir Robert Robinson who said 〔Molecular structure of Strychnine, Brucine and Vomicine, R. Robinson, Prog. Org. Chem., 1952,1 ,2〕 ''for its molecular size it is the most complex substance known''. ==The molecule== :Strychnine numbering conventions The C21H22N2O2 strychnine molecule contains 7 rings including an indoline system. It has a tertiary amine group, an amide, an alkene and an ether group. The naturally occurring compound is also chiral with 6 asymmetric carbon atoms including one quaternary one. :Strychnine, functional groups 抄文引用元・出典: フリー百科事典『 ウィキペディア（Wikipedia）』 ■ウィキペディアで「Strychnine total synthesis」の詳細全文を読む スポンサード リンク
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