Peterson烯化反应

α-硅基碳负离子和羰基化合物反应先得到β-羟基硅烷，接着通过酸碱催化下消除得到烯烃的反应，称为Peterson烯化反应。此反应也被称为硅Wittig反应。最早由Peterson在1968年报道。

与Wittig反应相比此反应具有很多优点：1、α-硅基碳负离子比磷叶立德具有更高的反应活性；2、此反应比具有更高的Z-选择性；3、没有磷副产物生成，后处理更加简便。但是α-硅基碳负离子相对难以得到，限制了此反应的应用。

反应机理

在碱性条件下，为順式消除，主要得到Z构型烯烃。

在酸性条件下，为反式消除，主要得到E构型烯烃。

反应实例

【Org. Lett. 2003, 5, 1697-1700】

【J. Fluorine Chem.2003, 124, 81-84】

【Org. Lett. 2004, 6, 3917-3920】

【J. Am. Chem. Soc.2007, 129, 13366】

【Org. Lett. 2013, 15, 3086-3089】

【Org. Lett., 2002, 4, 4329-4331】

【Synlett, 2003, 414-416】

【Synthesis, 2000, 1223-1228】

【Synthesis, 2000, 1223-1228】

【Synlett, 2006, 2577-2580】

【Org. Lett., 2016, 18, 336-339】

【J. Org. Chem., 2014, 79, 1145-1155】

A solution of 1.5 mmol ethyl trimethylsilanylacetate and 2.0 mmol chiral pinacol methyl ether in 6.0 mL toluene was added to a solution of LDA (1.6 mmol) in 5.0 mL toluene at −78◦C. The mixture was stirred at −20◦C for 1 h and cooled to −78◦C again. Then a solution of 1.0 mmol 4-tert-butyl-cyclohexanone in 4 mL toluene was added dropwise over a period of 3 min, and the resulting mixture was stirred at room temperature for 5 h. Upon removal of the solvent, the residue was purified by silica gel column chromatography to afford 68% of (S)-(+)-ethyl (4-tert-butylcyclohexylidene)acetate as a colorless oil, with 19% e.e.

【Org. Lett., 2002, 4, 4329】

To 2.5 mL THF solution containing 0.26 g α-trimethylsilyl selenoacetamide (1.05 mmol) was added 0.625 mL 1.6 M n-BuLi (1.0 mmol) at 0◦C; the mixture was stirred for 15 min. Then 0.12 mL o-tolualdehyde (1.0 mmol) was added; the reaction mixture instantly changed to reddish orange. After being stirred at room temperature for an additional hour, the reaction mixture was poured onto water and extracted with CH2Cl2. The organic layer was dried over MgSO4 and concentrated in vacuo. The residue was purified by silica gel column chromatography using hexane/dichloromethane as an eluent to give 0.258 g (E)-1-(3-(2- methylphenyl)-1-selenoxo-2-propenyl)pyrrolidine as a reddish orange solid, in a yield of 93%, m.p. 137–140◦C.

【J. Org. Chem., 2003, 68, 7979】

参考文献

一、Name Reactions （A Collection of Detailed Reaction Mechanisms）, Jie Jack Li, Peterson olefination，page 476-477.

二、Organic Chemistry Portal：http://www.organic-chemistry.org/namedreactions/peterson-olefination.shtm

三、Comprehensive Organic Name Reactions and Reagents, by Zerong Wang，2176-2179