From 1,2-difunctionalisation to cyanide-transfer cascades – Pd-catalysed cyanosulfenylation of internal (oligo)alkynes

Bürger, Marcel; Loch, Maximilian N.; Jones, Peter G.; Werz, Daniel B.

doi:10.1039/c9sc04569d

Cited by 26 publications

(16 citation statements)

References 59 publications

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“…[47c] A sulfur-based polycycle synthesis (198) was recently demonstrated via a thiopalladation, double insertion into unsaturation, and a cyanide transfer in a cascade process (10-99 % yields). [48] Cyanoselenylation via a similar pathway was also reported to access selenoenol ethers. [49] Matsude et al [50] recently demonstrated a cascade cyclization of optically active 1,1-diarylmethylcarbonates 199 via Mizoroki-Heck followed by Suzuki coupling to furnish trans-1,2disubstituted indanes 200 (Scheme 30).…”

Section: Electrophilic Activation/reductive Elimination Cà C Bond Formation Via Nucleopalladationmentioning

confidence: 90%

Exploiting the Versatility of Palladium Catalysis: A Modern Toolbox for Cascade Reactions

et al. 2021

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Dedicated to Professor S. Chandrasekaran on the occasion of his 75 th birthday.Palladium-catalyzed cascade cyclization received much attention in organic synthesis due to its efficiency and rapid transformation of simple starting materials into complex molecular skeletons. Celebrating the 10 th year of the prestigious Nobel prize for palladium chemistry, we witness it still proceeds strong over other transition metals for its versatility. Cascade reactions in contemporary organic synthesis reduced cost and time through careful design. It has emerged as the first choice, a powerful tool for multiple bond formations in one step with a wide range of functional group tolerance due to the deep understanding of various pathways. A variety of compounds with biological relevance with complex molecular scaffolds have been achieved using these cascade coupling reactions. This review outlines Pd-catalyzed cascade reactions from the post-Nobel era. Nevertheless, more discoveries and endless possibilities for new transformations are underway.

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Section: Electrophilic Activation/reductive Elimination Cà C Bond Formation Via Nucleopalladationmentioning

confidence: 90%

Exploiting the Versatility of Palladium Catalysis: A Modern Toolbox for Cascade Reactions

et al. 2021

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“…Recently, the realm of cyano-functionalization was further explored by Werz and coworkers by palladium catalysis and was utilized for the cyanosulfenylation 56 and cyanoselenylation 57 of internal alkynes independently in 2020 (Scheme 56). Both aromatic and aliphatic thiocyanates underwent the syn-1,2cyanosulfenylation of internal alkynes and could access the tetra-substituted double bonds with sulphur and cyano in adjacent positions.…”

Section: Alkenyl and Alkynyl C-h Cyanationmentioning

confidence: 99%

C–CN bond formation: an overview of diverse strategies

et al. 2021

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“…Very recently, Werz and co-workers described the first example of Pd-catalyzed intramolecular cyanosulfenylation of a triple bond and applied this method to the synthesis of two medium-sized heterocycles 47, one oxathiocin and one oxathionin (Scheme 18) [55]. Mechanistically, the sequence consists of a thiopalladation-cyanide transfer cascade.…”

Section: C-s Bond Formationmentioning

confidence: 99%

Synthesis of Medium-Sized Heterocycles by Transition-Metal-Catalyzed Intramolecular Cyclization

et al. 2020

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Medium-sized heterocycles (with 8 to 11 atoms) constitute important structural components of several biologically active natural compounds and represent promising scaffolds in medicinal chemistry. However, they are under-represented in the screening of chemical libraries as a consequence of being difficult to access. In particular, methods involving intramolecular bond formation are challenging due to unfavorable enthalpic and entropic factors, such as transannular interactions and conformational constraints. The present review focuses on the synthesis of medium-sized heterocycles by transition-metal-catalyzed intramolecular cyclization, which despite its drawbacks remains a straightforward and attractive synthesis strategy. The obtained heterocycles differ in their nature, number of heteroatoms, and ring size. The methods are classified according to the metal used (palladium, copper, gold, silver), then subdivided according to the type of bond formed, namely carbon–carbon or carbon–heteroatom.

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From 1,2-difunctionalisation to cyanide-transfer cascades – Pd-catalysed cyanosulfenylation of internal (oligo)alkynes

Abstract: The intra- and intermolecular Pd-catalysed cyanosulfenylation of internal alkynes enables the formation of tetrasubstituted thioacrylonitriles and is extended to oligoyne systems leading to oligoenes and a cyanide transfer over four or six atoms.

Cited by 26 publications

References 59 publications

Exploiting the Versatility of Palladium Catalysis: A Modern Toolbox for Cascade Reactions

Exploiting the Versatility of Palladium Catalysis: A Modern Toolbox for Cascade Reactions

C–CN bond formation: an overview of diverse strategies

Synthesis of Medium-Sized Heterocycles by Transition-Metal-Catalyzed Intramolecular Cyclization

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