Organopalladium Intermediates in Coordination-Directed C(sp3)-H Functionalizations

Suseelan, Anjana Sarala; Dutta, Arnab; Lahiri, Goutam Kumar

doi:10.1016/j.trechm.2020.11.009

Cited by 13 publications

(4 citation statements)

References 93 publications

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“…The C( sp 3 )−H bonds are inert and robust in comparison to the aromatic counterparts, which makes their functionalizations rather difficult. The low reactivity could be due to their high bond energies (typically 90–100 kcal/mol), low acidity (estimated pKa=45–60) and the lack of active HOMO or LUMO to interact with transition‐metal‐catalytic centers [82] . In addition, the very subtle energy differences among different C( sp 3 )−H bonds present in a complex organic molecule make it difficult to achieve site selectivity and often lead to the formation of mixtures [83] .…”

Section: Transition‐metal‐catalyzed C(sp3)−h Alkynylationmentioning

confidence: 99%

Transition‐Metal‐Catalyzed Selective Alkynylation of C−H Bonds

et al. 2021

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Alkynylation reactions are one of the most sought‐after synthetic methodologies due to the versatility of C−C triple bond diversifications. Sonogashira coupling was widely used for the synthesis of alkynylated molecules; however, this methodology requires the use of previously halogenated substrates, which is a major drawback. To overcome this issue, a complimentary method, transition‐metal‐catalyzed C−H alkynylation, was emerged as an alternative tool in the recent years. Though the initial reports required the use of either specific directing groups or strong alkynylating agents for effective functionalization, recent studies indicate that transition‐metal‐catalyzed site selective alkynylations can be carried out using mild and readily available alkynylating agents under moderate reaction conditions. In this review, we explain the transition metal cataluyzed site selective alkynylation both C(sp2)−H and C(sp3)−H bonds by emphasizing to the reaction mechanism.

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Section: Transition‐metal‐catalyzed C(sp3)−h Alkynylationmentioning

confidence: 99%

Transition‐Metal‐Catalyzed Selective Alkynylation of C−H Bonds

et al. 2021

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“…Among these, transition-metal-catalyzed asymmetric C–H functionalization reactions have provided powerful access to the synthesis of diverse enantioenriched compounds in a highly enantioselective manner. − Generally speaking, there are three different pathways for achieving asymmetric C–H functionalization reactions, desymmetrization, kinetic resolution, and the addition to unsaturated compounds (Scheme ). Asymmetric C–H functionalization reactions can be catalyzed by various transition-metal complexes including palladium (Pd), − rhodium (Rh), − iridium (Ir), − ruthenium (Ru), − and other 3d transition metals. − Among these, Pd and Rh catalysts have received the most attention due to their applications in diverse enantioselective reactions with broad substrate scope. In this regard, Pd-catalyzed asymmetric C–H functionalization reactions have been extensively investigated and well-reviewed.…”

Section: Introductionmentioning

confidence: 99%

Rhodium-Catalyzed Asymmetric C–H Functionalization Reactions

Liu,

Yin,

Zhao

et al. 2023

Chem. Rev.

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This review summarizes the advancements in rhodium-catalyzed asymmetric C–H functionalization reactions during the last two decades. Parallel to the rapidly developed palladium catalysis, rhodium catalysis has attracted extensive attention because of its unique reactivity and selectivity in asymmetric C–H functionalization reactions. In recent years, Rh-catalyzed asymmetric C–H functionalization reactions have been significantly developed in many respects, including catalyst design, reaction development, mechanistic investigation, and application in the synthesis of complex functional molecules. This review presents an explicit outline of catalysts and ligands, mechanism, the scope of coupling reagents, and applications.

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“…In a stark contrast to aromatic C( sp 2 )–H olefination, distal C( sp 3 )-H olefination is still an underexplored territory due to its intrinsic problem − and is mostly restricted to aliphatic acids as substrates. − Although in 2016 Shi and co-workers reported δ -alkenylation of leucine and its derivatives, internal alkynes were used as the source of olefin . While olefins are widely used in cycloaddition chemistry, − distal aliphatic olefination possess two-fold issues: (i) requirement of six-membered metallacycle overriding thermodynamically stable five membered cycle and (ii) postsynthetic easy cyclization in the presence of a more nucleophilic directing group which eventually diminishes the versatility of the olefin group inserted …”

Section: Introductionmentioning

confidence: 99%

“…distal aliphatic olefination possess two-fold issues: (i) requirement of sixmembered metallacycle overriding thermodynamically stable five membered cycle49 and (ii) postsynthetic easy cyclization in…”

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confidence: 99%

Simplifying the Synthesis of Nonproteinogenic Amino Acids via Palladium-Catalyzed δ-Methyl C–H Olefination of Aliphatic Amines and Amino Acids

Bhattacharya

Baroliya

Al‐Thabaiti

2023

JACS Au

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Transition metal-catalyzed directing group assisted C− H functionalizations provide a straightforward access to a wide variety of nonproteinogenic amino acids. While altering the side chain of an existing natural amino acids is one way, introducing a functional group to an aliphatic amine to synthesize versatile unnatural amino acids is another exciting avenue. In this work, we explore both the possibilities by the palladium-catalyzed δ-C(sp 3 )−H olefination of aliphatic amines and amino acids. A diverse substrate scope including sequential difunctionalizations followed by post synthetic transformations were achieved to understand the applicability of the current protocol. An indepth mechanistic study was carried out to learn the mode of the reaction pathway.

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Organopalladium Intermediates in Coordination-Directed C(sp3)-H Functionalizations

Cited by 13 publications

References 93 publications

Transition‐Metal‐Catalyzed Selective Alkynylation of C−H Bonds

Transition‐Metal‐Catalyzed Selective Alkynylation of C−H Bonds

Rhodium-Catalyzed Asymmetric C–H Functionalization Reactions

Simplifying the Synthesis of Nonproteinogenic Amino Acids via Palladium-Catalyzed δ-Methyl C–H Olefination of Aliphatic Amines and Amino Acids

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