Clive-Reich-Sharpless烯合成反应

有机硒醚类化合物氧化为硒亚砜后，经过顺式消除得到烯烃的反应。常见的氧化剂：NaIO4，H2O2，m-CPBA，过氧乙酸和二甲基过氧化酮。

反应机理

分子内的顺式消除机理

反应实例

Cyclohex-2-en-1-one (4). 1 (1 equiv), AgOCOCF3 (1.2 equiv) and phenylselenyl bromide (1.1 equiv) in ether at 0 C afforded after hydrolysis 2 in 70% yield. Oxidation of 2 with NaIO4 gave 4 (92%).

【Clive DLJ, JCS Chem Comm, 1973, 695】

Acrylophenone (7). To a solution of LDA under N2 in THF was added 1,4-diphenyl-1-butanone 5. After 10 min stirring, phenylselenyl bromide was added dropwise at -78 C. To the solution at 0 C,

H2O2 was added and the mixture was stirred for 30 min at r.t. Workup and chromatography afforded 7 in 85% yield.

【Reich HJ, J Am Chem Soc, 1973, 95, 5813】

1-Dodecene (11). To a solution of selenide 10 (0.2 mmol) in MeOH/THF/H2O containing NaHCO3 (3 equiv) at 20 C was added NaIO4 (0.3 mmol). After 6 h, the reaction mixture was evaporated in vacuo. Usual workup afforded the olefin 11 in 62% yield.

【Sharpless KB, J Org Chem, 1975, 40, 947】

【Callant, Paul; Ongena, Raymond; Vandewalle, Maurits (January 1981). 'Iridoids : Novel total synthesis of (±)- isoiridomyrmecin and of (±)-verbenalol'. Tetrahedron. 37 (11): 2085–2089.】

【Waring, Anthony John; Zaidi, Javid Hussain (1985). 'Synthesis of a 4-acylcyclohexa-2,5-dienone: 3,4-dihydro-3,3,8a-trimethyl-naphthalene-1,6(2H,8aH)-dione'. Journal of the Chemical Society, Perkin Transactions 1: 631.】

相关文献

1 Clive DLJ JCS Chem Comm 1973 695

2 Reich HJ J Am Chem Soc 1973 95 5813

3 Sharpless KB J Org Chem 1975 40 947

4 Clive DLJ Tetrahedron 1978 34 1049

5 Friedrich LE J Org Chem 1981 46 306

6 Kutney JP Can J Chem 1983 61 1111

7 Krief A Bull Soc Chim Fr 1997 134 869

8 Clive DLJ J Am Chem Soc 1998 120 10332

9 Pattenden G Org Biomol Chem 2009 7 4448

10 Magnus P J Am Chem Soc 2009 131 16045

11 Franck X Tet Lett 2009 50 4554

编译自：Organic Syntheses Based On Name Reactions, 3RdEd, A. Hassner, Page 91.