The Shapiro reaction or tosylhydrazone decomposition is an organic reaction in which a ketone or aldehyde is converted to an alkene through an intermediate hydrazone in the presence of 2 equivalents of organolithium reagent.[1][2][3] The reaction was discovered by Robert H. Shapiro in 1967.[4] The Shapiro reaction was used in the Nicolaou Taxol total synthesis.[5] This reaction is very similar to the Bamford–Stevens reaction, which also involves the basic decomposition of tosyl hydrazones.
The Shapiro reaction
^Shapiro, R. H.; Lipton, M. F.; Kolonko, K. J.; Buswell, R. L.; Capuano, L. A. (1975). "Tosylhydrazones and alkyllithium reagents: More on the regiospecificity of the reaction and the trapping of three intermediates". Tetrahedron Lett.16 (22–23): 1811–1814. doi:10.1016/S0040-4039(00)75263-4.
^Shapiro, Robert H. (1976). "Alkenes from Tosylhydrazones". Org. React.23 (3): 405–507. doi:10.1002/0471264180.or023.03. ISBN 978-0471264187.
^Adlington, Robert M.; Barret, Anthony G. M. (1983). "Recent applications of the Shapiro reaction". Acc. Chem. Res.16 (2): 55–59. doi:10.1021/ar00086a004.
^Shapiro, Robert H.; Heath, Marsha J. (1967). "Tosylhydrazones. V. Reaction of Tosylhydrazones with Alkyllithium Reagents. A New Olefin Synthesis". J. Am. Chem. Soc.89 (22): 5734–5735. doi:10.1021/ja00998a601.
^Nicolaou, Kyriacos C.; Sorensen, Erik J. (1996). Classics in Total Synthesis: Targets, Strategies, Methods. Wiley. ISBN 9783527292318.
The Shapiroreaction or tosylhydrazone decomposition is an organic reaction in which a ketone or aldehyde is converted to an alkene through an intermediate...
transmetalation. This method can be used for preparing vinyllithium. In the Shapiroreaction, two equivalents of strong alkyllithium base react with p-tosylhydrazone...
Benjamin Aaron Shapiro (born January 15, 1984) is an American lawyer, columnist, author, and conservative political commentator. He writes columns for...
ring C. Two key chemical transformations are the Shapiroreaction and the pinacol coupling reaction. The overall synthesis was published in 1995 in a...
the Shapiroreaction, and the Bamford-Stevens reaction to vinyl compounds. Hydrazones can also be synthesized by the Japp–Klingemann reaction via β-keto...
hydrazones. When derived from ketones, these hydrazones participate in the Shapiroreaction and the Eschenmoser–Tanabe fragmentation. 2,4,6-Triisopropylbenzenesulfonylhydrazide...
tosylhydrazone, using sodium methoxide (the Bamford–Stevens reaction) or an alkyllithium (the Shapiroreaction). The formation of longer alkenes via the step-wise...
catalysis. Hydrolysis is the reverse reaction of formation with regeneration of the carbonyl compound. In the Shapiroreaction tosylhydrazones are used as a...
19. Ring A (12) and ring C (19) reacted together to alcohol 20 in a Shapiroreaction (tBuLi, CeCl3) in a similar way as in the Nicolaou Taxol total synthesis...
The Ullmann reaction or Ullmann coupling, named after Fritz Ullmann, couples two aryl or alkyl groups with the help of copper. The reaction was first reported...
the prayer, arguing sexism as the reason for misattribution, while Fred Shapiro, with greater nuance, has alternated in his conclusions, but presents both...
molecular biology, proposed by James A. Shapiro in 1979, in which the transposable element is duplicated during the reaction, so that the transposing entity is...
Susan Cabot (born Harriet Pearl Shapiro; July 9, 1927 – December 10, 1986) was an American film, stage, and television actress. She rose to prominence...
Ehud Shapiro (Hebrew: אהוד שפירא; born 1955) is an Israeli scientist, entrepreneur, artist, and political activist who is Professor of Computer Science...
Jonathan Shapiro (born 27 October 1958) is a South African cartoonist, known as Zapiro, whose work appears in numerous South African publications and...
In turbomachinery, degree of reaction or reaction ratio (R) is defined as the ratio of the static pressure rise in the rotating blades of a compressor...
Shapiro & Glebbeek 1995, pp. 238–240. Cross 2005, pp. 236–237. Shadwick 2003, p. 186. Shadwick 2003, p. 186; Shapiro & Glebbeek 1995, p. 358. Shapiro...
Global Information