尽管烯烃伴侣与各种亲电试剂的赫克反应取得了巨大成功，但该变体侧重于碳═杂原子的对应物仍然难以捉摸。
该文中，研究人员报道了N-[（Z）-3-碘烯丙基]-氨基乙醛和水合肼（NH2NH2–H2O）的Pd（0）催化的不对称分子内腙型Heck反应，其中所需的腙是通过酸促进的缩合原位产生的。这种Heck范式的一个关键战略优势是，所得到的Heck产物烯丙基二氮烯快速进行立体特异性脱氮[1,5]-σ-迁移重排，最终提供具有高对映选择性的3-取代四氢吡啶（THP）的多米诺序列。底物诱导的非对映选择性也已经实现，只产生顺式-2,5-二取代的THPs。
研究人员通过多种有价值的生物活性靶标的正式合成证明了该序列的实用性，包括3-乙基吲哚喹啉嗪、precamol和尼拉帕尼。
附：英文原文
Title: Domino Sequences Involving Stereoselective Hydrazone-Type Heck Reaction and Denitrogenative [1,5]-Sigmatropic Rearrangement
Author: Shuling Yu, Lijin Zhou, Sihan Ye, Xiaofeng Tong
Issue&Volume: March 27, 2023
Abstract: Although the Heck reactions of alkene partners with various electrophiles have achieved great success, the variant focused on carbon═heteroatom counterparts still remains elusive. Herein, we report a Pd(0)-catalyzed asymmetric intramolecular hydrazone-type Heck reaction of N-[(Z)-3-iodoallyl]-aminoacetaldehyde and hydrazine hydrate (NH2NH2–H2O), wherein the required hydrazone is in situ generated via an acid-promoted condensation. A key strategic advantage of this Heck paradigm is that the resultant Heck product allylic diazene rapidly undergoes stereospecific denitrogenative [1,5]-sigmatropic rearrangement, eventually furnishing a domino sequence toward 3-substituted tetrahydropyridine (THP) with high enantioselectivity. The substrate-induced diastereoselective version has also been realized, exclusively giving cis-2,5-disubstituted THPs. The utility of this sequence is demonstrated by the formal synthesis of multiple valuable bioactive targets, including 3-ethylindoloquinolizine, preclamol, and niraparib.
DOI: 10.1021/jacs.3c01075
