EPOXIDATION OF ENOL SILYL ETHERS, PHOSPHATES, ESTERS, AND LACTONES BY DIMETHYLDIOXIRANE
EPOXIDATION OF ENOL SILYL ETHERS, PHOSPHATES, ESTERS, AND LACTONES BY DIMETHYLDIOXIRANE
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DOI：
10.1002/cber.19911241033
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发表时间：
1991-10-01
期刊：
影响因子：
--
通讯作者：
WANG, XH
中科院分区：
文献类型：
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作者：
ADAM, W;HADJIARAPOGLOU, L;WANG, XH
用分离的二甲基二氧环烷(4)（作为丙酮溶液）进行环氧化反应，得到烯醇硅基醚1a、b、烯醇磷酸1c-k、烯醇酯和内酯1l-u的环氧化物2a-u（表1）。这些不稳定的环氧化物（在0℃以下稳定）可以以纯形式分离出来并进行光谱表征（IR， H-1和C-13 NMR）。p-u的导数足够稳定，甚至可以进行C、H分析。升温至室温导致相应的-氧官能化羰基产物的重排3。由于环氧化物2c具有足够的抗水解性，因此可以采用原位法制备。
The epoxides 2a-u (Table 1) of the enol silyl ethers 1a,b, enol phosphates 1c-k, and enol esters and lactones 1l-u were prepared in excellent yields by epoxidation with isolated dimethyldioxirane (4) (as acetone solution). These labile epoxides (stable below 0-degrees-C) could be isolated in pure form and characterized spectroscopically (IR, H-1 and C-13 NMR). The derivatives 2p-u were sufficiently stable so that even C,H analyses were obtained. Warming up to room temperature led to rearrangement to the corresponding alpha-oxy-functionalized carbonyl products 3. Since epoxide 2c was sufficiently resistant towards hydrolysis, it could be prepared by the in situ method.