- Nickel-Catalyzed Deaminative Acylation of Activated Aliphatic Amines with Aromatic Amides via C-N Bond Activation
-
Deaminative functionalization of aliphatic primary amines has great synthetic utility. Herein, we describe a Ni-catalyzed reductive deaminative cross-electrophile coupling reaction between Katritzky salts and aromatic amides. This work provides examples of the synthesis of various ketones from alkylpyridinium salts, including both primary and secondary alkylamines. Given its mild reaction conditions and high functional group tolerance, this cross-coupling strategy is expected to be useful for late-stage functionalization of complex compounds.
- Yu, Chu-Guo,Matsuo, Yutaka
-
p. 950 - 955
(2020/02/15)
-
- Water Phase, Room Temperature, Ligand-Free Suzuki–Miyaura Cross-Coupling: A Green Gateway to Aryl Ketones by C–N Bond Cleavage
-
We report herein a green strategy for synthesis of aryl ketones from twisted amides by using Pd(OAc)2 as catalysts. This method shows high functional group tolerance to offer a variety of ketones in good yields under mild conditions (up to 94 %). Notably, this methodology demonstrates the first water phase, room temperature, ligand-free Suzuki–Miyaura coupling through C–N bond cleavage, which is environmentally friendly and might facilitate the development of amide based green chemistry.
- Zhang, Yuqi,Wang, Zijia,Tang, Zhao,Luo, Zhongfeng,Wu, Hongxiang,Liu, Tingting,Zhu, Yulin,Zeng, Zhuo
-
p. 1620 - 1628
(2020/03/04)
-
- Synergistic Activation of Amides and Hydrocarbons for Direct C(sp3)–H Acylation Enabled by Metallaphotoredox Catalysis
-
The utilizations of omnipresent, thermodynamically stable amides and aliphatic C(sp3)?H bonds for various functionalizations are ongoing challenges in catalysis. In particular, the direct coupling between the two functional groups has not been realized. Here, we report the synergistic activation of the two challenging bonds, the amide C?N and unactivated aliphatic C(sp3)?H, via metallaphotoredox catalysis to directly acylate aliphatic C?H bonds utilizing amides as stable and readily accessible acyl surrogates. N-acylsuccinimides served as efficient acyl reagents for the streamlined synthesis of synthetically useful ketones from simple C(sp3)?H substrates. Detailed mechanistic investigations using both computational and experimental mechanistic studies were performed to construct a detailed and complete catalytic cycle. The origin of the superior reactivity of the N-acylsuccinimides over other more reactive acyl sources such as acyl chlorides was found to be an uncommon reaction pathway which commences with C?H activation prior to oxidative addition of the acyl substrate.
- Baik, Mu-Hyun,Choi, Seulhui,Hong, Soon Hyeok,Lee, Geun Seok,Won, Joonghee
-
supporting information
p. 16933 - 16942
(2020/08/03)
-
- N-Acylsuccinimides: Efficient acylative coupling reagents in palladium-catalyzed Suzuki coupling via C–N cleavage
-
An acylative Suzuki coupling of activated amides with aryl boronic acids has been reported via palladium-catalyzed C–N bond cleavage. This protocol demonstrate amides can be activated by an atom-economic and cheap succinimide, which can be efficiently utilized to synthesize broad array of diaryl ketones in moderate to good yields.
- Cui, Ming,Chen, Zeyu,Liu, Tingting,Wang, Hui,Zeng, Zhuo
-
supporting information
p. 3819 - 3822
(2017/09/15)
-
- Nickel-Catalyzed Negishi Cross-Coupling of N -Acylsuccinimides: Stable, Amide-Based, Twist-Controlled Acyl-Transfer Reagents via N-C Activation
-
This paper reports a room temperature, nickel-catalyzed Negishi cross-coupling of N -acylsuccinimides with arylzinc reagents via selective N-C bond cleavage enabled by amide bond twist. The reaction proceeds using a commercially available, air-stable Ni(II) precatalyst in the absence of additives under exceedingly mild conditions. Of broad interest, this report introduces N -acylsuccinimides as stable, crystalline, electrophilic, cost-effective, benign, amide-based acyl transfer reagents via acyl metal intermediates. The reaction selectivity is governed by half-twist of the amide bond in N -acylsuccinimides, thus opening the door for applications in metal-catalyzed manifolds via redox-neutral reaction pathways tuneable by amide bond distortion.
- Shi, Shicheng,Szostak, Michal
-
supporting information
p. 3602 - 3608
(2017/08/15)
-
- N-Acylsuccinimides: Twist-controlled, acyl-transfer reagents in Suzuki-Miyaura cross-coupling by N-C amide bond activation
-
The palladium-catalyzed Suzuki-Miyaura cross-coupling of N-acylsuccinimides as versatile acyl-transfer reagents via selective amide N-C bond cleavage is reported. The method is user-friendly since it employs commercially-available, air-stable reagents and catalysts. The cross-coupling is enabled by half-twist of the amide bond in N-acylsuccinimides. These highly effective, crystalline acyl-transfer reagents present major advantages over perpendicularly twisted N-acylglutarimides, including low price of the succinimide activating ring, selective metal insertion under redox neutral conditions and high stability of the amide bond towards reaction conditions. Mechanistic studies indicate that oxidative addition is the rate limiting step in this widely applicable protocol.
- Osumi, Yuki,Liu, Chengwei,Szostak, Michal
-
supporting information
p. 8867 - 8871
(2017/11/09)
-