Regio- and diastereoselective decarboxylative coupling of heteroaromatic alkanes
Regio- and diastereoselective decarboxylative coupling of heteroaromatic alkanes
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DOI：
10.1021/ja070116w
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发表时间：
2007-04-11
影响因子：
15
通讯作者：
Tunge, Jon A.
中科院分区：
文献类型：
--
作者：
Waetzig, Shelli R.;Tunge, Jon A.
杂芳烷烃的烯丙基酯进行容易的钯催化脱羧偶联。所得C-C键以高非对映选择性和高区域选择性形成，用于在更取代的烯丙基末端偶联。有人提出，这种不寻常的组合的选择性的结果从串联烯丙基化/氮杂-Cope重排序列。烯丙基化后，脱羧脱芳构化产生氮杂-Cope重排的中间体。随后的aza-Cope重排在温和条件下发生，因为它是由rearomatization驱动的。
Allylic esters of heteroaromatic alkanes undergo facile palladium-catalyzed decarboxylative coupling. The resulting C-C bond is formed with high diastereoselectivity and high regioselectivity for coupling at the more substituted allyl terminus. It is proposed that this unusual combination of selectivities results from a tandem allylation/aza-Cope rearrangement sequence. After allylation, decarboxylative dearomatization produces an intermediate for the aza-Cope rearrangement. The subsequent aza-Cope rearrangement occurs under mild conditions because it is driven by rearomatization.