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Dual Role of the Rhodium(III) Catalyst in C-H Activation: [4 + 3] Annulation of Amide with Allylic Alcohols to 7-Membered Lactams.
J Org Chem. 2021 03 19; 86(6):4625-4637.JO

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.

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Publisher Full Text (DOI)

Authors+Show Affiliations

Sherikar MS
Department of Organic Chemistry, Indian Institute of Science, Bangalore 560 012, Karnataka, India.
Devarajappa R
Department of Organic Chemistry, Indian Institute of Science, Bangalore 560 012, Karnataka, India.
Prabhu KR
Department of Organic Chemistry, Indian Institute of Science, Bangalore 560 012, Karnataka, India.

MeSH

AmidesCatalysisLactamsPropanolsRhodium

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

33689338

Citation

Sherikar, Mahadev Sharanappa, et al. "Dual Role of the Rhodium(III) Catalyst in C-H Activation: [4 + 3] Annulation of Amide With Allylic Alcohols to 7-Membered Lactams." The Journal of Organic Chemistry, vol. 86, no. 6, 2021, pp. 4625-4637.
Sherikar MS, Devarajappa R, Prabhu KR. Dual Role of the Rhodium(III) Catalyst in C-H Activation: [4 + 3] Annulation of Amide with Allylic Alcohols to 7-Membered Lactams. J Org Chem. 2021;86(6):4625-4637.
Sherikar, M. S., Devarajappa, R., & Prabhu, K. R. (2021). Dual Role of the Rhodium(III) Catalyst in C-H Activation: [4 + 3] Annulation of Amide with Allylic Alcohols to 7-Membered Lactams. The Journal of Organic Chemistry, 86(6), 4625-4637. https://doi.org/10.1021/acs.joc.1c00048
Sherikar MS, Devarajappa R, Prabhu KR. Dual Role of the Rhodium(III) Catalyst in C-H Activation: [4 + 3] Annulation of Amide With Allylic Alcohols to 7-Membered Lactams. J Org Chem. 2021 03 19;86(6):4625-4637. PubMed PMID: 33689338.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Dual Role of the Rhodium(III) Catalyst in C-H Activation: [4 + 3] Annulation of Amide with Allylic Alcohols to 7-Membered Lactams. AU - Sherikar,Mahadev Sharanappa, AU - Devarajappa,Ravi, AU - Prabhu,Kandikere Ramaiah, Y1 - 2021/03/09/ PY - 2021/3/11/pubmed PY - 2021/7/3/medline PY - 2021/3/10/entrez SP - 4625 EP - 4637 JF - The Journal of organic chemistry JO - J Org Chem VL - 86 IS - 6 N2 - [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. SN - 1520-6904 UR - https://www.unboundmedicine.com/medline/citation/33689338/Dual_Role_of_the_Rhodium_III__Catalyst_in_C_H_Activation:_[4_+_3]_Annulation_of_Amide_with_Allylic_Alcohols_to_7_Membered_Lactams_ DB - PRIME DP - Unbound Medicine ER -