Regioselective Pd-Catalyzed Carbopalladation/Decarboxylative Allylic Alkynylation of <i>ortho</i>-Iodoallenamides with Alkynyl Carboxylic Acids

Hédouin, Jonathan; Carpentier, Vincent; Renard, Romain M. Q.; Schneider, Cédric; Gillaizeau, Isabelle; Hoarau, Christophe

doi:10.1021/acs.joc.9b01408

Cited by 22 publications

(10 citation statements)

References 68 publications

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“…Nevertheless, only one instance of this kind of activation has been recently reported by Schneider, Gillaizeau, Horau, and co-workers that consists of a decarboxylative allylic alkynylation event. 117 This methodology can be employed to synthesize both six-and five-membered heterocycles bearing a propynyl unit (64d and 64e, respectively). Based on previous studies, a possible mechanism was proposed, which initiated with oxidative addition of tethered aryl halide to Pd(0) precatalyst, generating the Pd(II) species 64f.…”

Section: Assisting Functionality In An Allenementioning

confidence: 99%

Intermolecular Allene–Alkyne Coupling: A Significantly Useful Synthetic Transformation

Pradhan,

Park

2024

ACS Catal.

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Because of its wide applicability in the synthesis of diverse unsaturated building blocks, allene−alkyne (AA) coupling has emerged as a powerful methodology to drive useful chemical transformations in the past two decades. Considering recent discoveries in this active research area, in this Review, we aim to support chemists in the selection of suitable methods, particularly intermolecular approaches, according to the synthesis needs. However, inherent similarities between the reactivities of π-systems create considerable obstacles while predicting selectivity in an intermolecular platform. Therefore, herein, intermolecular couplings for the chemoselective, stereoselective, and regioselective syntheses of acyclic and cyclic C-skeletons are reviewed. However, considering the lack of a well-organized review in this field, we initially provide a brief historical overview of the types of thermally induced reactions that are mostly feasible for electronically biased coupling components and are nonselective. Subsequently, emerging selective strategies are described, which include activator-controlled and neighboring functional group-assisted regio-, stereo-, and π-skeleton-divergent processes. Overall, this Review is divided into two parts. In the first part, strategies for the fabrication of acyclic C-skeletons are explained according to the reaction types. In the second part, synthetic transformations affording cyclic structures are reviewed based on the substrate class (that is, nonassisted and assisted substrates). Key reaction intermediates of each subset of coupling and factors affecting productselective discrimination of the active species with the highlight of rationale are systemically summarized. Understanding of these substrate structure-and catalyst-dependent factors provides insights into the regulation of the chemoselectivities of title AA crosscouplings and, therefore, the design of alternative catalytic routes with distinct mechanistic features.

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Section: Assisting Functionality In An Allenementioning

confidence: 99%

Intermolecular Allene–Alkyne Coupling: A Significantly Useful Synthetic Transformation

Pradhan,

Park

2024

ACS Catal.

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“…79 Recently, Hoarau and co-workers described a regioselective domino carbopalladation/decarboxylative allylic alkynylation sequence of ortho-iodoallenamides 193 with alkynyl carboxylic acids under palladium catalysis (Scheme 64). 80 The reaction provides access to propargyl-functionalized isoquinolinones 194 or indoles by either six-membered or five-membered N-heterocyclic ring formation, respectively. The production of ortho-iodoallenamides 195 in situ with subsequent formation of the π-allyl-Pd complex and a decarboxylative allylic alkynylation process was also realized to deliver propargyl-functionalized 194 in a more convenient and one-pot manner directly starting from N-propargylated amides (Scheme 65).…”

Section: Organic and Biomolecular Chemistry Reviewmentioning

confidence: 99%

Recent advances in catalytic decarboxylative transformations of carboxylic acid groups attached to a non-aromatic sp²or sp carbon

Rahaman¹,

Chauhan²,

Bhadra³

2023

Org. Biomol. Chem.

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“…Activated N-allenyl-2-iodoanilines 103 and propynoic acids 104 allowed the rapid construction of 3-propargylindoles 105 via the formation of a -allyl-Pd(II) intermediate, that in turn, undergoes a decarboxylative allylic alkynylation step (Scheme 39). 42 To promote the process in higher yields, the use of an additive (PivOH) was crucial in stabilizing the -allyl-Pd(II) intermediate.…”

Section: Scheme 38 Dihydrobenzoindole Derivatives Via Alkyne Insertiomentioning

confidence: 99%

Pd-Catalyzed Domino Reactions Involving Alkenes To Access Substituted Indole Derivatives

et al. 2020

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Palladium-catalyzed domino reactions are advanced tools in achieving various nitrogen-containing heterocycles in an efficient and economical manner due to the reduced number of steps in the process. This review highlights recent advances in domino processes aimed at the synthesis of indole derivatives and polycyclic systems containing the indole nucleus in intra/intra- or intra/intermolecular reactions. In particular, we consider domino processes that involve a double bond in a step of the sequence, which allow the issue of regioselectivity in the cyclization to be faced and overcome. The different sections in this review focus on the synthesis of the indole nucleus and functionalization of the scaffold starting from different substrates that have been identified as activated starting materials, which involve a halogenated moiety or unactivated unsaturated systems. In the former case, the reaction is under Pd(0) catalysis, and in the second case a Pd(II) catalytic species is required and then an oxidant is necessary to reconvert the Pd(0) into the active Pd(II) species. On the other hand, the second method has the advantage that it uses easy available and inexpensive substrates.1 Introduction2 Indole Scaffold Synthesis2.1 Activated Substrates2.2 Unactivated Substrates3 Functionalization of Indole Scaffold3.1 Activated Substrates3.2 Unactivated Substrates4 Conclusions

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Regioselective Pd-Catalyzed Carbopalladation/Decarboxylative Allylic Alkynylation of ortho-Iodoallenamides with Alkynyl Carboxylic Acids

Cited by 22 publications

References 68 publications

Intermolecular Allene–Alkyne Coupling: A Significantly Useful Synthetic Transformation

Intermolecular Allene–Alkyne Coupling: A Significantly Useful Synthetic Transformation

Recent advances in catalytic decarboxylative transformations of carboxylic acid groups attached to a non-aromatic sp²or sp carbon

Pd-Catalyzed Domino Reactions Involving Alkenes To Access Substituted Indole Derivatives

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Regioselective Pd-Catalyzed Carbopalladation/Decarboxylative Allylic Alkynylation of ortho-Iodoallenamides with Alkynyl Carboxylic Acids

Cited by 22 publications

References 68 publications

Intermolecular Allene–Alkyne Coupling: A Significantly Useful Synthetic Transformation

Intermolecular Allene–Alkyne Coupling: A Significantly Useful Synthetic Transformation

Recent advances in catalytic decarboxylative transformations of carboxylic acid groups attached to a non-aromatic sp2or sp carbon

Pd-Catalyzed Domino Reactions Involving Alkenes To Access Substituted Indole Derivatives

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Recent advances in catalytic decarboxylative transformations of carboxylic acid groups attached to a non-aromatic sp²or sp carbon