Nickel-Catalyzed Reductive Asymmetric Aryl-Acylation and Aryl-Carbamoylation of Unactivated Alkenes

Abstract

Herein we reported a nickel-catalyzed asymmetric two-component reductive aryl-acylation and arylcarbamoylation of aryl iodide-tethered unactivated alkenes, which utilize ortho-pyridinyl esters and isocyanates as the electrophilic acyl sources, respectively. Under the catalysis of a nickel-Pyrox complex with zinc powder as the reductant, a variety of chiral indanes, indolines, and dihydrobenzofurans bearing a quaternary stereogenic center were prepared in moderate to high efficiency and good to excellent enantioselectivities. The utility of this method is demonstrated by various simple derivatizations of the attached carbonyl group, particularly the sequential benzylic oxidation and pinacol coupling, which provides a concise entry to benzene-fused bicyclic bridged ring framework containing three challenging tetrasubstituted stereocenters in high stereocontrol.

Electrochemical Fe-catalysed radical cyclization for the synthesis of oxindoles

“…These reaction outcomes are consistent with the radical nature of the reaction. Moreover, N-arylacrylamides containing a wide range of synthetically versatile functional groups such as halides (11)(12)(13)(14), cyanide (15), ketone (18), and medicinally attractive trifluoromethyl (16) and trifluoromethoxyl (17) groups could be successfully incorporated under the electrocatalytic conditions, generating the corresponding oxindoles with good reaction yield. While alkyl and aryl substituents on nitrogen seem to have no significant effect on the reaction efficiency (19)(20)(21), N-H ( 22) free or N-Tos (23) arylacrylamide is not applicable under the current conditions.…”

“…In particular, methods for sustainable and efficient preparation of carbonyl-containing oxindoles are extremely attractive as these core structures are found in a wide variety of natural products and can be used as key intermediates in total synthesis of indole alkaloids (Scheme 1A). [8][9][10][11][12][13][14] As an elegant example, the groups of Yu and Kong recently reported a nickel-catalysed asymmetric reductive carbo-carboxylation of N-arylacrylamides with CO 2 as the carboxyl source, and the obtained products could be applied in the synthesis of a series of natural products. 15 However, the necessity for the use of stoichiometric amounts of zinc as a metal reductant may compromise its practical adoption.…”

Recent Advances in Ni-Catalyzed Asymmetric Reductive Difunctionalization of Alkenes

“…2021 年, 王川课题组 [21] 进一步延伸了镍催化非活 化烯烃的不对称还原环化双碳官能团化的反应研究, 成 功合成了含季碳手性中心的芳基酰基化产物和芳基酰 胺化产物(Scheme 30). 该反应分别以邻吡啶酯和异氰 酸酯为亲电酰基源.…”

“…1.12 烯烃的不对称还原芳基-氨基化反应 之前的报道均是烯烃分子内的不对称双碳化反应, 杂原子亲电试剂的使用鲜有报道. 2021 年, 南京大学朱 少林课题组 [22] 图式 30 镍催化烯烃的还原芳基酰基化 [21] Scheme 30 Ni-catalyzed aryl-acylation of alkenes 图式 31 镍催化烯烃的芳基氨基化反应 [22] Scheme 31 Ni-catalyzed aryl-amination of alkenes 有机化学 综述与进展 下, 可以顺利地获得各类具有立体季碳中心的 β-手性胺 衍生物. 该反应底物范围广泛, 芳香环上带有给电子取 代基和吸电子取代基的芳基碘化物, 都能以中等到良好 化学选择性(42%～78%)和高立体选择性(88%～99% ee) 得到芳基氨基化产物.…”

Nickel-Catalyzed Regioselective Reductive Ring Opening of Aryl Cyclopropyl Ketones with Alkyl Bromides

“…As a continuation of our ongoing interest in developing new reductive cross-coupling reactions, we turned our attention to utilizing easily accessible electrophilic alkyl halides as the coupling partner with aryl cyclopropyl ketones. Under reductive nickel catalysis, this alkylative ring opening reaction features complete regiocontrol on C–C bond cleavage, efficient Csp 3 –Csp 3 bond formation, as well as the merits of high step-economy and functionality tolerance (Scheme C).…”