有機(jī)硒醚類化合物氧化為硒亞砜后，經(jīng)過順式消除得到烯烴的反應(yīng)。常見的氧化劑：NaIO4，H2O2，m-CPBA，過氧乙酸和二甲基過氧化酮。
反應(yīng)機(jī)理
分子內(nèi)的順式消除機(jī)理
反應(yīng)實(shí)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.】
【W(wǎng)aring, 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.】
相關(guān)文獻(xiàn)
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
編譯自：Organic Syntheses Based On Name Reactions, 3RdEd, A. Hassner, Page 91.
