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      Traditional and sustainable approaches for the construction of C–C bonds by harnessing C–H arylation

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          Abstract

          Biaryl scaffolds are found in natural products and drug molecules and exhibit a wide range of biological activities. In past decade, the transition metal-catalyzed C–H arylation reaction came out as an effective tool for the construction of biaryl motifs. However, traditional transition metal-catalyzed C–H arylation reactions have limitations like harsh reaction conditions, narrow substrate scope, use of additives etc. and therefore encouraged synthetic chemists to look for alternate greener approaches. This review aims to draw a general overview on C–H bond arylation reactions for the formation of C–C bonds with the aid of different methodologies, majorly highlighting on greener and sustainable approaches.

          Abstract

          Transition-metal-catalyzed C–H arylations are an effective tool for the construction of biaryl motifs in an efficient and selective manner. Here the authors provide an overview of the state-of-the-art of the field and perspectives on emerging directions toward increased sustainability.

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          Organic Photoredox Catalysis.

          In this review, we highlight the use of organic photoredox catalysts in a myriad of synthetic transformations with a range of applications. This overview is arranged by catalyst class where the photophysics and electrochemical characteristics of each is discussed to underscore the differences and advantages to each type of single electron redox agent. We highlight both net reductive and oxidative as well as redox neutral transformations that can be accomplished using purely organic photoredox-active catalysts. An overview of the basic photophysics and electron transfer theory is presented in order to provide a comprehensive guide for employing this class of catalysts in photoredox manifolds.
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            Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds

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              Analysis of Past and Present Synthetic Methodologies on Medicinal Chemistry: Where Have All the New Reactions Gone?

              An analysis of chemical reactions used in current medicinal chemistry (2014), three decades ago (1984), and in natural product total synthesis has been conducted. The analysis revealed that of the current most frequently used synthetic reactions, none were discovered within the past 20 years and only two in the 1980s and 1990s (Suzuki-Miyaura and Buchwald-Hartwig). This suggests an inherent high bar of impact for new synthetic reactions in drug discovery. The most frequently used reactions were amide bond formation, Suzuki-Miyaura coupling, and SNAr reactions, most likely due to commercial availability of reagents, high chemoselectivity, and a pressure on delivery. We show that these practices result in overpopulation of certain types of molecular shapes to the exclusion of others using simple PMI plots. We hope that these results will help catalyze improvements in integration of new synthetic methodologies as well as new library design.
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                Author and article information

                Contributors
                dmaiti@chem.iitb.ac.in
                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group UK (London )
                2041-1723
                28 February 2022
                28 February 2022
                2022
                : 13
                : 1085
                Affiliations
                GRID grid.417971.d, ISNI 0000 0001 2198 7527, Department of Chemistry, , Indian Institute of Technology Bombay, ; Powai, Mumbai, 400076 India
                Author information
                http://orcid.org/0000-0001-8353-1306
                Article
                28707
                10.1038/s41467-022-28707-9
                8885660
                35228555
                aeb7affc-4466-4847-9293-f6cf7c0c7a82
                © The Author(s) 2022

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

                History
                : 13 April 2021
                : 27 January 2022
                Funding
                Funded by: FundRef https://doi.org/10.13039/501100001843, DST | Science and Engineering Research Board (SERB);
                Award ID: CRG/2018/003915
                Award Recipient :
                Categories
                Review Article
                Custom metadata
                © The Author(s) 2022

                Uncategorized
                homogeneous catalysis,synthetic chemistry methodology
                Uncategorized
                homogeneous catalysis, synthetic chemistry methodology

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