Burgess試劑，即N-(三乙基銨磺酰)氨基甲酸甲酯，是一個(gè)氨基甲酸酯類的內(nèi)鹽，用作有機(jī)化學(xué)中的脫水劑。它可溶于大多數(shù)有機(jī)溶劑中，CAS號(hào)為51373-37-6。Burgess脫水試劑是非常有效的由仲醇和叔醇脫水制備烯烴的試劑，反應(yīng)溫和，有選擇性。但一級(jí)醇反應(yīng)效果不佳。β位消除，遵循熱消除Ei機(jī)理（消除過(guò)程中，兩種離去基團(tuán)同時(shí)離去，互相之間又迅速成鍵）。
試劑的制備：
(a) Burgess, E. M.; Penton, H. R., Jr.; Taylor, E. A.; Williams, W. M. Org. Synth. Coll. Edn. 1987, 6, 788–791. (b) Duncan, J. A.; Hendricks, R. T.; Kwong, K. S. J. Am.Chem. Soc. 1990, 112, 8433–8442.
反應(yīng)機(jī)理
先和醇反應(yīng)生成磺酸酯，接著β位消除，遵循熱消除Ei機(jī)理。
Khapli, S.; Dey, S.; Mal, D. J. Indian Inst. Sci. 2001, 81, 461–476. (Review).
反應(yīng)實(shí)例
對(duì)于伯醇一般是更容易發(fā)生取代反應(yīng)，而不是消除脫水。
【Wipf, P.; Xu, W. J. Org. Chem. 1996, 61, 6556–6562.】
該試劑不僅能用于烯的合成，也能用于腈，異腈以及氧化腈的合成。此外它還被用于合成雜環(huán)惡唑啉和噻唑啉。
【W(wǎng)ipf, P.; Fritch, P. C. Tetrahedron Lett. 1994, 35, 5397】
To a flamedried reaction vessel equipped witha stir bar and septum was added 4-(4-nitrophenyl)butan-1-ol (0.21 mL, 1.25mmol) followed by a benzene solution of 1 (5.0 mL, 1.25 mmol, 0.25 M).The septum was then removed and quickly replaced with a Teflon cap prior to thereaction being placed into a 50°C bath. After 1 h, the bath temperature wasincreased to 85°C and a small aliquot of the reaction mixture was removed tocheck for the formation of the initial adduct 2 (LC/MSgenerally shows M++18(H2O): 426). The reaction was stirred for 12–16 h and thenperiodically monitored, by LC/MS, for the disappearance of 2.(CAUTION: Remove the reaction vessel from the heating bath and allow itstemperature to drop below the boiling point of the solvent prior to removing ananalytical sample.) Frequently, LC/MS spectra obtained prior towork-up show numerous side products that disappear after work-up. Aftercomplete disappearance of 2, the reaction was cooled to ambienttemperature, benzene was removed in vacuo, and the residue was partitionedbetween EtOAc and 0.5 M HCl. The organic layer was washed with 5% sodiumbicarbonate and brine, then dried over sodium sulfate. Filtration, solventremoval and silica gel chromatography (10–60% EtOAc in hexanes, lineargradient) provided the target compound (318 mg, 77%) as a white solid.
【Tetrahedron Letters 2002, 3887–3890】
Fredericamycin的合成【Kita, Y. et al. J. Am. Chem. Soc. 2001,123, 3214.】
Taxol的合成【Holton, R. A. et al. J. Am. Chem. Soc. 1994, 116, 1597. 】
Penitrem D的合成【Smith, A. B., III et al. J. Am. Chem. Soc. 2003, 125, 8228.】
【Miller, C. P.; Kaufman, D. H. Synlett 2000, 8, 1169–1171.】
Keller, L.; Dumas, F.; D’Angelo, J. Eur. J. Org. Chem. 2003, 2488–2497.
【Nicolaou, K. C.; Snyder, S. A.; Longbottom, D. A.; Nalbandian, A. Z.; Huang, X. Chem. Eur. J. 2004, 10, 5581–5606.】
參考文獻(xiàn)
一、Name Reactions （A Collection of Detailed Reaction Mechanisms）, Jie Jack Li, Burgess dehydrating reagent，page 95-96.
二、化學(xué)空間：http://www.chem-station.com/cn/reactions/%e6%b6%88%e9%99%a4%e5%8f%8d%e5%ba%94/2014/08/post-2566.html
