Diastereoselectivity of additions to chiral carbonyl oxides
Diastereoselectivity of additions to chiral carbonyl oxides
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DOI：
10.1021/jo00130a021
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发表时间：
1995-12-15
影响因子：
3.6
通讯作者：
Zope, UR
中科院分区：
文献类型：
--
作者：
Dussault, PH;Zope, UR
研究了立体中心对羰基氧化物生成过氧氢缩醛的影响。将甲醇或2-丙醇加成到8-苯基丙醛O-氧化物中具有适度的立体选择性;将叔醇加成到8-苯基丙醛O-氧化物中具有更高的选择性。通过官能化氢过氧缩醛转化为1，2-二氧六环证实的产物立体化学被发现来自通过Felkin-Anh型过渡态的亲核攻击。捕获含有相邻氢键供体的羰基氧化物对于顺式和反式羰基氧化物异构体都具有适度的选择性。3-（三烷基甲锡烷基）-1-烯醇醚的臭氧分解通过可能的过氧化乙烯的中间作用而进行，同时损失了带有甲锡烷基的碳。
The influence of a resident stereocenter on the formation of hydroperoxy acetals from carbonyl oxides is investigated. Addition of either methanol or 2-propanol to 8-phenylpropanal O-oxide proceeds with modest stereoselectivity; addition of a tertiary alcohol proceeds with higher selectivity. Product stereochemistry, which is confirmed by conversion of a functionalized hydroperoxy acetal to a 1,2-dioxane, is found to derive from nucleophilic attack through a Felkin-Anh type transition state. Trapping of a carbonyl oxide containing a neighboring hydrogen bond donor proceeds with modest selectivity for both syn- and anti-carbonyl oxide isomers. Ozonolysis of a 3-(trialkylstannyl)-1-enol ether proceeds with loss of the stannyl-bearing carbon through the possible intermediacy of a vinyl peroxide.