Ni-Catalyzed Reductive Arylcyanation of Alkenes

Abstract

We disclose a Ni-catalyzed reductive arylcyanation of alkene using environmentally benign and nontoxic organo cyanating reagent N-cyano-N-phenyl-p-toluenesulfonamide. This reaction provides a new method for the rapid synthesis of cyanosubstituted oxindoles and isoquinoline-1,3-diones and features high functional group tolerance. In addition, an enantioselective version was developed for the construction of enantiomerically enriched 3-cyanomethyl oxindole. This method has also been applied to the synthesis of natural alkaloids (+)-esermethole and (+)-physostigmine.

Nickel-catalyzed asymmetric reductive arylcyanation of alkenes with acetonitrile as the cyano source

“…Based on the moderate 47% yield with ligand L6, further optimization of the yield with ligand L6 was conducted. The addition of a base was found to increase the yields (entries [11][12][13][14][15]. The screening of various organic and inorganic bases showed that Et 3 N as a base furnished 2a with 81% yield and 92% ee (entry 11).…”

“…Over the past decades, many non-enantioselective approaches have been developed for preparing cyano-substituted oxindoles. In this regard, Grigg, 8 Zhu, 9 Lautens, 10 Sun, 11 Kong, 12 and other groups 13 made great contributions, and they used KCN, K 4 [Fe(CN) 6 ], Zn(CN) 2 and BnSCN as the cyano sources. However, highly enantioselective catalytic cyanation reactions that can construct all-carbon quaternary chiral centers are quite scarce because of the stronger coordination ability of cyanide anions than the chiral ligands.…”

Visible-light-induced radical cascade reaction to prepare oxindoles via alkyl radical addition to N-arylacryl amides

“…Esermethole and physostigmine could be prepared from amine 14 according to the reported procedures. 14,55,56…”

Recent Advances in Ni-Catalyzed Asymmetric Reductive Difunctionalization of Alkenes

“…NiBr 2 (dme) (15 mol%) ent-L2 (15 mol%) Zn (4 equiv. ), 40 o C DMA (0.4 mol/L), 10 h 51% ~ 75% yield 17% ~ 95% ee 图式 24 镍催化 1,6-二烯的去对称化还原环化反应 [17] Scheme 24 Ni-catalyzed desymmetric reductive cyclization of 1,6-dienes 1.9 烯烃的不对称还原芳基-氰基化反应 2021 年, 孔望清课题组 [18] 使用环境无害且无毒的 有机物氰化试剂 N-氰基-N-苯基-对甲苯磺酰胺(NCTS) 作为氰基源, 发展了镍催化烯烃的还原环化芳基氰基化 反应. 该反应具有较高的官能团耐受性, 为快速合成氰 基取代羟吲哚类和异喹啉-1,3-二酮类衍生物提供了一 种新方法.…”

“…该反应分别以邻吡啶酯和异氰 酸酯为亲电酰基源. 值得注意的是, 作者还测试了其他 图式 25 镍催化烯烃的芳基氰基化反应 [18] Scheme 25 Ni-catalyzed aryl-cyanation of alkenes [19] Scheme 26 Ni-catalyzed carbo-carboxylation of alkenes 图式 27 (-)-Debromoflustramine B 的合成 [19] Scheme 27 Synthesis of (-)-debromoflustramine B 图式 28 (＋)-Coixspirolactam A 的合成 [19] Scheme 28 Synthesis of (＋)-coixspirolactam A [20] Scheme 29 Ni-catalyzed carbo-carboxylation of alkenes 多种亲电酰基化试剂, 包括酰基氯化物、酰基氟化物、 酸酐和硫酯, 但未能得到预期的产物.…”