776-75-0Relevant academic research and scientific papers
A practical modification of the Barton-McCombie reaction and radical O- to S- rearrangement of xanthates
Quiclet-Sire, Beatrice,Zard, Samir Z.
, p. 9435 - 9438 (1998)
The C-O bond in xanthates derived from carbohydrates can be reductively cleaved by heating in 2-propanol in the presence of equimolar amounts of dilauroyl peroxide, added in small portions; if benzene is used as the solvent, an O- to S- rearrangement of the xanthate occurs.
Microwave assisted, palladium catalyzed aminocarbonylations of heteroaromatic bromides using solid Mo(CO)6 as the carbon monoxide source
Letavic, Michael A.,Ly, Kiev S.
, p. 2339 - 2343 (2007)
The direct conversion of a variety of heteroaromatic bromides into heteroaromatic amides is described. This reaction utilizes Mo(CO)6 as the carbon monoxide source and is performed using microwave heating allowing for very short reaction times. This convenient methodology allows for the preparation of a variety of heteroaromatic amides useful in medicinal chemistry applications.
TBAI-catalyzed C–N bond formation through oxidative coupling of benzyl bromides with amines: a new avenue to the synthesis of amides
Kumar, Dhirendra,Maury, Suresh Kumar,Kumari, Savita,Kamal, Arsala,Singh, Himanshu Kumar,Singh, Sundaram,Srivastava, Vandana
supporting information, p. 424 - 432 (2022/02/09)
A new green approach for the synthesis of amide through TBAI-catalyzed oxidative coupling of benzyl bromides with amine was developed in the presence of tert-butyl hydroperoxide (TBHP) as an oxidant. Various electron-donating and withdrawing groups containing benzyl bromides and various amines, were subjected to the reaction and transformed to the corresponding amide in good to excellent yields.
Catalytic N-Acylation of Cyclic Amines by Arylglyoxylic Acids via Radical-Radical Cross-Coupling
Bhadra, Sukalyan,Gupta, Aniket,Kumar Singh, Anupam,Rahaman, Ajijur
, p. 2198 - 2202 (2021/07/22)
A methodical mechanistic investigation allowed for the catalytic N-acylation of secondary cyclic amine counterparts by arylglyoxylic acids through radical-radical coupling. The reaction proceeds via a twofold SET-promoted Cu(I)/Cu(II) catalytic cycle under mild conditions. An analogous reaction variant allows for the N-acylation in a one-pot fashion directly starting from a secondary cyclic amine even in the presence of a second amine or hydroxy group.
Deoxygenative hydroboration of primary, secondary, and tertiary amides: Catalyst-free synthesis of various substituted amines
An, Duk Keun,Jaladi, Ashok Kumar,Kim, Hyun Tae,Yi, Jaeeun
supporting information, (2021/11/17)
Transformation of relatively less reactive functional groups under catalyst-free conditions is an interesting aspect and requires a typical protocol. Herein, we report the synthesis of various primary, secondary, and tertiary amines through hydroboration of amides using pinacolborane under catalyst-free and solvent-free conditions. The deoxygenative hydroboration of primary and secondary amides proceeded with excellent conversions. The comparatively less reactive tertiary amides were also converted to the corresponding N,N-diamines in moderate yields under catalyst-free conditions, although alcohols were obtained as a minor product.
A practical and sustainable protocol for direct amidation of unactivated esters under transition-metal-free and solvent-free conditions
Chen, Cheng,Cheng, Hua,Du, Min-Chen,Qian, Liang,Qin, Xin,Sang, Wei,Yao, Wei-Zhong,Yuan, Ye,Zhang, Rui
supporting information, p. 3972 - 3982 (2021/06/17)
In this paper, a NaOtBu-mediated synthesis approach was developed for direct amidation of unactivated esters with amines under transition-metal-free and solvent-free conditions, affording a series of amides in good to excellent yields at room temperature. In particular, an environmentally friendly and practical workup procedure, which circumvents the use of organic solvents and chromatography in most cases, was disclosed. Moreover, the gram-scale production of representative products3a,3wand3auwas efficiently realized by applying operationally simple, sustainable and practical procedures. Furthermore, this approach was also applicable to the synthesis of valuable molecules such as moclobemide (a powerful antidepressant), benodanil and fenfuram (two commercial agricultural fungicides). These results demonstrate that this protocol has the potential to streamline amide synthesis in industry. Meanwhile, quantitative green metrics of all the target products were evaluated, implying that the present protocol is advantageous over the reported ones in terms of environmental friendliness and sustainability. Finally, additional experiments and computational calculations were carried out to elucidate the mechanistic insight of this transformation, and one plausible mechanism was provided on the basis of these results and the related literature reports.
Direct Amidation of Esters by Ball Milling**
Barreteau, Fabien,Battilocchio, Claudio,Browne, Duncan L.,Godineau, Edouard,Leitch, Jamie A.,Nicholson, William I.,Payne, Riley,Priestley, Ian
supporting information, p. 21868 - 21874 (2021/09/02)
The direct mechanochemical amidation of esters by ball milling is described. The operationally simple procedure requires an ester, an amine, and substoichiometric KOtBu and was used to prepare a large and diverse library of 78 amide structures with modest to excellent efficiency. Heteroaromatic and heterocyclic components are specifically shown to be amenable to this mechanochemical protocol. This direct synthesis platform has been applied to the synthesis of active pharmaceutical ingredients (APIs) and agrochemicals as well as the gram-scale synthesis of an active pharmaceutical, all in the absence of a reaction solvent.
Iron-catalyzed oxidative amidation of acylhydrazines with amines
Wang, Yi-Jie,Zhang, Guo-Yu,Shoberu, Adedamola,Zou, Jian-Ping
supporting information, (2021/08/18)
A new approach for amide bond formation via a mild and efficient Iron-catalyzed cross-coupling reaction of acylhydrazines and amines using TBHP as oxidant is described. This protocol is compatible with a wide range of amines and acylhydrazines. In addition, the synthetic application of the reaction is presented.
Photocatalytic aldehydes/alcohols/toluenes oxidative amidation over bifunctional Pd/MOFs: Effect of Fe-O clusters and Lewis acid sites
Bian, Fengxia,Cheng, Hongmei,Jiang, Heyan,Sun, Bin,Tan, Jiangwei,Zang, Cuicui
, p. 279 - 287 (2021/08/21)
Heterogeneous photocatalytic organic synthesis is fascinating because of the utilization of ubiquitous solar light for chemical transformations. Here, three Fe-MOFs with different Fe-O clusters, Lewis acid sites and morphologies were synthesized through coordination structure engineering. Pd/Fe-MOFs nanocomposites were used to challenge the amide bond green synthesis with visible light. Pd/MIL-101(Fe) exhibited the best photocatalytic performance due to the easily excited Fe3-μ3-oxo clusters for light absorption, the efficient photogenerated carriers separation and migration, the large amount of Lewis acid sites based aldehydes and amines condensation promotion and the efficient O2 reduction to superoxide radicals over photogenerated electron-rich Pd NPs. Various aldehydes, alcohols and toluenes could be transformed to amide compounds with amines over Pd/MIL-101(Fe) with just oxygen or air as the green oxidant and water as the by-product. One-pot C–C cross-coupling and photo-redox C–N coupling cascade reactions could also be achieved over Pd/MIL-101(Fe). This work shed light on the efficient and sustainable amide bonds synthesis.
One-Pot Synthesis of Tertiary Amides from Organic Trichlorides through Oxygen Atom Incorporation from Air by Convergent Paired Electrolysis
Luo, Zhongli,Imamura, Kenji,Shiota, Yoshihito,Yoshizawa, Kazunari,Hisaeda, Yoshio,Shimakoshi, Hisashi
, p. 5983 - 5990 (2021/05/04)
A convergent paired electrolysis catalyzed by a B12 complex for the one-pot synthesis of a tertiary amide from organic trichlorides (R-CCl3) has been developed. Various readily available organic trichlorides, such as benzotrichloride and its derivatives, chloroform, dichlorodiphenyltrichloroethane (DDT), trichloro-2,2,2-trifluoroethane (CFC-113a), and trichloroacetonitrile (CNCCl3), were converted to amides in the presence of tertiary amines through oxygen incorporation from air at room temperature. The amide formation mechanism in the paired electrolysis, which was mediated by a cobalt complex, was proposed.
