Dual Role of the Rhodium(III) Catalyst in C-H Activation: [4 + 3] Annulation of Amide with Allylic Alcohols to 7-Membered Lactams

Sherikar, MS and Devarajappa, R and Prabhu, KR (2021) Dual Role of the Rhodium(III) Catalyst in C-H Activation: [4 + 3] Annulation of Amide with Allylic Alcohols to 7-Membered Lactams. In: Journal of Organic Chemistry, 86 (6). pp. 4625-4637.

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Abstract

4 + 3 annulation of primary and secondary benzamide and cinnamamide derivatives using allyl alcohol as a coupling partner catalyzed by Rh(III) is reported, where Rh(III) is playing a dual role of an oxidant and a catalyst for C-H activation. The Rh-catalyst oxidizes allyl alcohol to its carbonyl derivative, and the in situ-generated carbonyl compound reacts with benzamide in the presence of the Rh-catalyst, forming the corresponding alkylated products. Mechanistic studies show that AgSbF6 is also playing a dual role. Apart from being a halide scavenger, AgSbF6 catalyzes the cyclization of the alkylated product, forming the desired lactam. The current method has good synthetic application and is useful for synthesizing a few biologically active compounds that can act as the dopamine D3 receptor ligand, including berberine-like analogues. The deuteration study and control experiments helped us to propose the mechanism. ©

Item Type:	Journal Article
Publication:	Journal of Organic Chemistry
Publisher:	American Chemical Society
Additional Information:	The copyright for this article belongs to American Chemical Society.
Keywords:	Activation analysis; Amides; Amines; Antimony compounds; Bioactivity; Carbonyl compounds; Catalysis; Catalysts; Chemical activation; Fluorine compounds; Silver compounds, Allyl alcohols; Allylic alcohol; Biologically active compounds; Carbonyl derivatives; Control experiments; Mechanistic studies; Receptor ligands; Synthetic application, Rhodium compounds, 1 benzyl 4 methyl 1,5 dihydro 2h azepin 2 one; 1 benzyl 4 phenyl 1,5 dihydro 2h azepin 2 one; 1 methyl 4 (3 phenoxyphenyl) 1,5 dihydro 2h azepin 2 one; 1 methyl 4 (3 tolyl) 1,5 dihydro 2h azepin 2 one; 1 methyl 4 (4 tolyl) 1,5 dihydro 2h azepin 2 one; 1 methyl 4 (thiophen 2 yl) 1,5 dihydro 2h azepin 2 one; 1 methyl 4 phenyl 1,5 dihydro 2h azepin 2 one; 1 methyl 4 styryl 1,3 dihydro 2h azepin 2 one; 1 methyl 4 styryl 1,5 dihydro 2h azepin 2 one; 2 (3 oxopropyl) n phenylbenzamide; 2 benzyl 2,5 dihydro 1h benzocazepin 1 one; 2 methyl 2,3,4,5 tetrahydro 1h benzocazepin 1 one; 2 methyl 2,5 dihydro 1h benzocazepin 1 one; 2 methyl 2,5 dihydro 1h naphtho1,2 cazepin 1 one; 2 methyl 2,5 dihydro 1h naphtho2,3 cazepin 1 one; 2 phenyl 2,5 dihydro 1h benzocazepin 1 one; 2,3,4,5 tetrahydro 1h benzocazepin 1 one; 2,5 dihydro 1h benzocazepin 1 one; 2,5 dimethyl 2,5 dihydro 1h benzocazepin 1 one; 2,7 dimethyl 2,5 dihydro 1h benzocazepin 1 one; 2,8 dimethyl 2,5 dihydro 1h benzocazepin 1 one; 2,9 dimethyl 2,5 dihydro 1h benzocazepin 1 one; 4 (3 bromophenyl) 1 methyl 1,5 dihydro 2h azepin 2 one; 4 (3 chlorophenyl) 1 methyl 1,5 dihydro 2h azepin 2 one; 4 (4 methoxyphenyl) 1 methyl 1,5 dihydro 2h azepin 2 one; 4 bromo 3 methoxy 2 methyl 2,3,4,5 tetrahydro 1h benzocazepin 1 one; 6 bromo 2 methyl 2,5 dihydro 1h benzocazepin 1 one; 6 methoxy 2 methyl 2,5 dihydro 1h benzocazepin 1 one; 6,7,8 trimethoxy 2 methyl 2,5 dihydro 1h benzocazepin 1 one; 7 acetyl 2 methyl 2,5 dihydro 1h benzocazepin 1 one; 7 bromo 2 methyl 2,5 dihydro 1h benzocazepin 1 one; 7 fluoro 2 methyl 2,5 dihydro 1h benzocazepin 1 one; 7 iodo 2 methyl 2,5 dihydro 1h benzocazepin 1 one; 7 methoxy 2 methyl 2,5 dihydro 1h benzocazepin 1 one; 7 methoxy 2,5 dihydro 1h benzocazepin 1 one; 7 methyl 4,7 dihydro 8h thieno2,3 cazepin 8 one; 8 bromo 2 methyl 2,5 dihydro 1h benzocazepin 1 one; 8 methoxy 2 methyl 2,5 dihydro 1h benzocazepin 1 one; 9 chloro 2 methyl 2,5 dihydro 1h benzocazepin 1 one; alcohol derivative; aldehyde; allyl alcohol; benzamide derivative; berberine derivative; carbonyl derivative; cinnamamide derivative; cinnamic acid derivative; deuterium; dopamine 3 receptor; halide; lactam derivative; n (2 methyl 1 oxo 2,5 dihydro 1h benzocazepin 7 yl)acetamide; n benzyl 3 methyl 6 oxohept 2 enamide; n methyl 2 (5 oxopenta 1,3 dien 1yl)benzamide; oxidizing agent; rhodium; scavenger; unclassified drug, alkylation; allylation; Article; carbon nuclear magnetic resonance; catalyst; chemical structure; cyclization; oxidation; proton nuclear magnetic resonance; reaction analysis; scale up; synthesis
Department/Centre:	Division of Chemical Sciences > Organic Chemistry
Date Deposited:	22 Feb 2023 04:20
Last Modified:	22 Feb 2023 04:20
URI:	https://eprints.iisc.ac.in/id/eprint/80480

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