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Grant support

We thank the Spanish Ministerio de Economia y Competitividad (MINECO, Project CTQ2012-35790), and MINECO/FEDER, UE (Project CTQ2015-66954-P) for financial support. E.H. thanks the Gobierno Vasco for a predoctoral fellowship. N.R. thanks the MICINN for a Ramon y Cajal contract and the European Commission for a Marie Curie Foundation (CIG: CHAAS-304085). We also thank the Centro de Computacion Cientifica de la UAM for their generous allocation of computer time.

Analysis of institutional authors

Martínez Garzón, ángel ManuCorresponding Author

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May 13, 2022
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Palladium-Catalyzed Carbonylative Cyclization of Amines via gamma-C(sp(3))-H Activation: Late-Stage Diversification of Amino Acids and Peptides

Publicated to:Acs Catalysis. 6 (10): 6868-6882 - 2016-10-01 6(10), DOI: 10.1021/acscatal.6b01987

Authors: Hernando, Elier; Villalva, Julia; Manu Martinez, Angel; Alonso, Ines; Rodriguez, Nuria; Gomez Arrayas, Ramon; Carretero, Juan C

Affiliations

UAM, Dept Quim Organ, Madrid 28049, Spain - Author

Abstract

The selective gamma-C(sp(3))-H carbonylation of N-(2-pyridyl)sulfonyl (N-SO2Py)-protected amines has been accomplished by using palladium catalysis and Mo(CO)(6) as carbonyl source. The reaction provides a powerful approach for derivatization of amine-based moieties, including amino acids, into richly functionalized gamma-lactams. Not only methyl groups, but also methylene C-H bonds of cyclopropanes and conformationally biased molecules can be activated to provide ring-fused gamma-lactam derivatives. This carbonylation protocol is also amenable to the late-stage diversification of more-complex multifunctional molecules such as dipeptides and tripeptides, demonstrating the key role of the N-SO2Py as directing group and its capacity to override other inherent substrate coordinating elements. In addition to providing an attractive solution to the difficulties in handling hazardous CO gas, the use of Mo(CO)(6) as an air-stable solid source of CO in substoichiometric amount (0.33 equiv) ensures Pd-II-catalytic activity by preventing its decomposition or deactivation under excess of CO via reduction of Pd-II to Pd-0 or saturation of the metal coordination sphere. Indeed, significantly lower efficiency is observed when the reactions are carried out under CO atmosphere (1 atm), or in the presence of increased amounts of Mo(CO)(6). A series of experimental and DFT mechanistic studies provide important insights about the reaction mechanism.

Keywords

2-pyridylsulfonylAliphatic amineAmino acidC(sp(2))-h bondsC-h carbonylationC-h functionalizationCarbon-monoxideCross-coupling reactionsDirect aerobic carbonylationDirecting groupsGamma-lactamN-(2-pyridyl)sulfonyl groupOrganic-synthesisOxidative carbonylationPalladium catalysisPeptideUnactivated c(sp(3))-h bonds

Quality index

Bibliometric impact. Analysis of the contribution and dissemination channel

The work has been published in the journal Acs Catalysis due to its progression and the good impact it has achieved in recent years, according to the agency WoS (JCR), it has become a reference in its field. In the year of publication of the work, 2016, it was in position 11/146, thus managing to position itself as a Q1 (Primer Cuartil), in the category Chemistry, Physical.

From a relative perspective, and based on the normalized impact indicator calculated from World Citations provided by WoS (ESI, Clarivate), it yields a value for the citation normalization relative to the expected citation rate of: 2.46. This indicates that, compared to works in the same discipline and in the same year of publication, it ranks as a work cited above average. (source consulted: ESI Nov 14, 2024)

This information is reinforced by other indicators of the same type, which, although dynamic over time and dependent on the set of average global citations at the time of their calculation, consistently position the work at some point among the top 50% most cited in its field:

  • Field Citation Ratio (FCR) from Dimensions: 16.99 (source consulted: Dimensions Jul 2025)

Specifically, and according to different indexing agencies, this work has accumulated citations as of 2025-07-09, the following number of citations:

  • WoS: 111

Impact and social visibility

From the perspective of influence or social adoption, and based on metrics associated with mentions and interactions provided by agencies specializing in calculating the so-called "Alternative or Social Metrics," we can highlight as of 2025-07-09:

  • The use, from an academic perspective evidenced by the Altmetric agency indicator referring to aggregations made by the personal bibliographic manager Mendeley, gives us a total of: 50.
  • The use of this contribution in bookmarks, code forks, additions to favorite lists for recurrent reading, as well as general views, indicates that someone is using the publication as a basis for their current work. This may be a notable indicator of future more formal and academic citations. This claim is supported by the result of the "Capture" indicator, which yields a total of: 52 (PlumX).

With a more dissemination-oriented intent and targeting more general audiences, we can observe other more global scores such as:

  • The Total Score from Altmetric: 3.

Leadership analysis of institutional authors

the author responsible for correspondence tasks has been Martínez Garzón, Ángel Manu.