Iodine monochloride-amine complexes: An experimental and computational approach to new chiral electrophiles
Iodine monochloride-amine complexes: An experimental and computational approach to new chiral electrophiles
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DOI：
10.1002/chem.200500507
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发表时间：
2005-09-19
影响因子：
4.3
通讯作者：
Wirth, T
中科院分区：
文献类型：
--
作者：
Haas, J;Bissmire, S;Wirth, T
内酯化反应是许多合成过程中的重要步骤。使用手性助剂或手性烯烃的底物控制反应已经被深入研究。本研究的重点是立体选择性试剂控制的碘内酯化，通过应用一种新的方法，使用一氯化碘和各种供体分子的配合物。(R)-1发现，2，3，4-四氢-1-萘胺和其它类似结构的胺在4-芳基-4-戊烯酸的碘环化反应中是有效的。对（R）-1，2，3，4-四氢-1-萘胺与XCl（X=I，H）的配合物进行了计算，以确定这些碘环化反应中可能的反应物种。在各种理论水平上进行了计算，包括使用碘的修改后的SDD基组的B3 LYP/6-31 + G（d，p）。
Lactonizations are important steps in many synthetic sequences. Substrate-controlled reactions that use chiral auxiliaries or chiral alkenes have already been studied in depth. This study focuses on stereoselective reagent-controlled iodolactonizations, by application of a new method that uses complexes of iodine monochloride and various donor molecules. (R)-1,2,3,4-Tetrahydro-l-naphthylamine and other amines with similar structures were found to be efficient in the iodocyclization of 4-aryl-4-pentenoic acids. Calculations were performed on complexes of (R)-1,2,3,4-tetrahydro-l-naphthylamine with XCl (X=I, H) to identify possible reactive species in these iodo-cyclizations. Calculations were carried out at various levels of theory, including B3LYP/6-31 + G (d,p) by using a modified SDD basis set for iodine.