四川大学刘小华研究团队报道了乙烯基α-重氮化合物重排不对称催化合成烯丙基亚砜酰胺。相关研究成果发表在2024年9月03日出版的国际学术期刊《德国应用化学》。

烯丙基亚砜亚胺的不对称重排是合成烯丙基亚磺酰胺等有吸引力的靶标的有效途径。目前的方法仅限于手性烯丙基亚磺酰亚胺前体的手性转移。

该文中，研究人员报告了一种获得光学富集的烯丙基亚磺酰胺，及其衍生物的通用且全新的重排路线。该过程涉及S-烷基化和不寻常的S-to-N重排步骤。手性镍配合物能够在温和条件下转化广泛的亚磺酰胺和乙烯基α-重氮吡唑酰胺。

研究人员合成了各种烯丙基亚磺酰胺，具有优异的γ-区域选择性和对映选择性，可以有效地转化为亚磺酰胺和4-氨基丁酸衍生物。此外，DFT计算证明了镍乙烯基卡宾的自旋态和构象之间的联系，以及未知的重排过程。

附：英文原文

Title: Asymmetric Catalytic Synthesis of Allylic Sulfenamides from Vinyl α-Diazo Compounds by a Rearrangement Route

Author: Zhijie Xiao, Maoping Pu, Yuzhen Li, Wei Yang, Fei Wang, Xiaoming Feng, Xiaohua Liu

Issue&Volume: 03 September 2024

Abstract: The asymmetric rearrangement of allylic sulfilimines is an effective route to synthetic attractive targets such as allylic sulfenamides and others. The current methods are limited to chirality transfer from chiral allylic sulfilimine precursors. Herein, we report a general and fundamentally new rearrangement route accessing optically enriched allylic sulfenamides and their derivatives. The process involves a S-alkylation and an unusual S-to-N rearrangement step. The chiral nickel complex enables the transformation of a broad scope of sulfenamides and vinyl α-diazo pyrazoleamides under mild conditions. Various allylic sulfenamides have been synthesized with excellent γ-regioselectivity and enantioselectivity, which can be efficiently converted to sulfinamide and 4-aminobutenoic acid derivatives. In addition, DFT calculations demonstrate the connection between the spin state and conformation of nickel vinyl carbenoid, as well as an unknown rearrangement process.

DOI: 10.1002/anie.202414712

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202414712