Borinic Acid Catalysed Reduction of Tertiary Amides with Hydrosilanes: A Mild and Chemoselective Synthesis of Amines

α-Tertiary amides are of great importance for medicinal chemistry. However, they are often challenging to access through conventional methods due to reactivity and chemoselectivity issues. Here we report a single-step approach towards such amides via cobalt-catalyzed intermolecular oxidative hydroamidation of unactivated alkenes, using nitriles of either solvent- or reagent-quantities. This protocol is orthogonal to groups that rapidly react under known carbocation amidation conditions such as tertiary alcohols, electron-rich alkenes, ketals, weak C−H bonds, and carboxylic acids. Straightforward access to a diverse array of hindered amides is demonstrated, including a rapid synthesis of an aminoadamantane-derived pharmaceutical intermediate.

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Highly Chemoselective Synthesis of Hindered Amides via Cobalt-Catalyzed Intermolecular Oxidative Hydroamidation

10.26434/chemrxiv.13285484 ◽

2020 ◽

Author(s):

Yun-Nian Yin ◽

Rui-Qi Ding ◽

Dong-Chen Ouyang ◽

Qing Zhang ◽

Rong Zhu

Keyword(s):

Carboxylic Acids ◽

Medicinal Chemistry ◽

Single Step ◽

Rapid Synthesis ◽

Tertiary Alcohols ◽

Chemoselective Synthesis ◽

Conventional Methods ◽

Tertiary Amides

α-Tertiary amides are of great importance for medicinal chemistry. However, they are often challenging to access through conventional methods due to reactivity and chemoselectivity issues. Here we report a single-step approach towards such amides via cobalt-catalyzed intermolecular oxidative hydroamidation of unactivated alkenes, using nitriles of either solvent- or reagent-quantities. This protocol is orthogonal to groups that rapidly react under known carbocation amidation conditions such as tertiary alcohols, electron-rich alkenes, ketals, weak C−H bonds, and carboxylic acids. Straightforward access to a diverse array of hindered amides is demonstrated, including a rapid synthesis of an aminoadamantane-derived pharmaceutical intermediate.

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A Direct, Versatile, and Chemoselective Synthesis of Vinylogous Bis- and Monourethanes/amides and β-Keto Esters by Aza-Knoevenagel-Type Reactions of Tertiary Amides with Enolates

European Journal of Organic Chemistry ◽

10.1002/ejoc.201601326 ◽

2017 ◽

Vol 2017 (3) ◽

pp. 582-592 ◽

Cited By ~ 13

Author(s):

Pei-Qiang Huang ◽

Wei Ou

Keyword(s):

Keto Esters ◽

Chemoselective Synthesis ◽

Tertiary Amides

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Chemoselective Synthesis of Aminobenzylic Derivative of Mackinazolinone and its X-ray Investigations

Journal of Chemistry and Chemical Sciences ◽

10.29055/jccs/703 ◽

2019 ◽

Vol 9 (3) ◽

pp. 109-114

Author(s):

Nuritdinova R. R. ◽

Elmuradov B. Zh. ◽

Okmanov R. Ya. ◽

Zakhidov K. A. ◽

Tadjimukhamedov Kh.S.

Keyword(s):

X Ray ◽

Chemoselective Synthesis

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Copper Catalysts in the Synthesis of Five-membered N-polyheterocycles

Current Organic Synthesis ◽

10.2174/1570179415666180815144442 ◽

2018 ◽

Vol 15 (7) ◽

pp. 940-971 ◽

Cited By ~ 9

Author(s):

Navjeet Kaur

Keyword(s):

Transition Metal ◽

Organic Synthesis ◽

Copper Catalysts ◽

Research Field ◽

Chemoselective Synthesis ◽

Specialized Equipment ◽

Transition Metal Catalyzed ◽

Synthetic Methodologies ◽

Metal Catalyzed ◽

Traditional Approaches

Background: Due to significant biological activity associated with N-, O- and S-heterocycles, a number of reports for their synthesis have appeared in recent decades. Traditional approaches require expensive or highly specialized equipment or would be of limited use to the synthetic organic chemist due to their highly inconvenient approaches. This review summarizes the applications of copper catalysts with the emphasis on their synthetic applications for nitrogen bearing polyheterocylces. In summary, this review article describes the synthesis of a number of five-membered poly heterocyclic rings. Objective: Nowadays new approaches that employ atom-economical and efficient pathway have been developed. The researchers are following natural models to design and synthesize heterocycles. The transition metal catalyzed protocols have attracted the attention as compared to other synthetic methodologies because they use easily available substrates to build multiple substituted complicated molecules directly under mild conditions. In organic synthesis, constituted by transition metal catalyzed coupling transformations are one of the most powerful and useful protocols. The N-heterocycles are synthesized by this convenient and useful tool. Conclusion: The efficient and chemoselective synthesis of heterocycles by this technique has appeared as an important tool. This review shows a highly dynamic research field and the employment of copper catalysts in organic synthesis. Several strategies have been pointed out in the past few years, to meet more sustainable, efficient and environmentally benign chemical products and procedures. The catalytic strategies have been the focus of intense research because they avoid the use of toxic reagents. Among these catalytic strategies, highly rewarding and an important method in heterocycles synthesis is metal catalyzed synthesis.

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Borinic acid catalyzed α-addition to isocyanide with aldehyde and water

Tetrahedron Letters ◽

10.1016/j.tetlet.2011.03.032 ◽

2011 ◽

Vol 52 (20) ◽

pp. 2557-2559 ◽

Cited By ~ 29

Author(s):

Takahiro Soeta ◽

Yuuki Kojima ◽

Yutaka Ukaji ◽

Katsuhiko Inomata

Keyword(s):

Acid Catalyzed ◽

Borinic Acid

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Lithium compound catalyzed deoxygenative hydroboration of primary, secondary and tertiary amides

Dalton Transactions ◽

10.1039/d1dt00364j ◽

2021 ◽

Vol 50 (7) ◽

pp. 2354-2358

Author(s):

Milan Kumar Bisai ◽

Kritika Gour ◽

Tamal Das ◽

Kumar Vanka ◽

Sakya S. Sen

Keyword(s):

Lithium Compound ◽

Tertiary Amides

A very simple and readily accessible lithium compound has been employed to catalyze the hydroboration of tertiary, secondary, and primary amides to the corresponding amines.

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