Factors Governing and Application of the Cope Rearrangement of 3,3-Dicyano-1,5-dienes and Related Studies
Factors Governing and Application of the Cope Rearrangement of 3,3-Dicyano-1,5-dienes and Related Studies
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DOI：
10.1021/acs.orglett.7b01951
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发表时间：
2017-08-04
期刊：
影响因子：
5.2
通讯作者：
Grenning, Alexander J.
中科院分区：
文献类型：
--
作者：
Fereyduni, Ehsan;Grenning, Alexander J.
科普和同事在20世纪40年代早期报道了3，3-二氰基-1，5-二烯的[3，3]重排（“The科普rearrangement”）。然而，直到最近，这些原始底物在很大程度上仍未被研究。在这里，我们探讨苯乙烯解共轭科普重排，非对映选择性的科普重排/解共轭α-烯丙基化序列，和控制因素α-与γ-烯丙基化区域选择性的Knoevenagel加合物烯丙基阴离子。最终，这些研究导致使用简单的化学方法从丰富的试剂合成多样化和功能密集的多环烷烃框架。
Cope and co-workers reported the [3,3] rearrangement of 3,3-dicyano-1,5-dienes in the early 1940s ("The Cope rearrangement"). However, these original substrates have remained largely unstudied until recently. Herein we explore styrene-deconjugating Cope rearrangements, a diastereoselective Cope rearrangement/deconjugative alpha-allylation sequence, and factors governing alpha- vs gamma-allylation regioselectivity of Knoevenagel adduct allyl anions. Ultimately, these studies result in the synthesis of diverse and functionally dense polycycloalkane frameworks from abundant reagents using simple chemistry.