Pd-catalyzed cascade reactions involving skipped dienes: from double carbopalladation to remote C–C cleavage

Azizollahi, Hamid; Mehta, Vaibhav P.; Garcı́a-López, José-Antonio

doi:10.1039/c9cc04817k

Cited by 13 publications

(12 citation statements)

References 57 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…After that, intermediate 38 participates in an uncommon β‐alkenyl rupture to generate complex 39 , and a 1,2‐migratory insertion affords structure 40 which can undergo a subsequent β‐H elimination process to end up in the synthesis of desired product 36 ( Scheme 6). [31] This reaction is a rare example of a β‐vinyl elimination which occurs from a quaternary carbon where no hydride elimination is possible.…”

Section: β‐Eliminations Cleaving C−c Bondsmentioning

confidence: 99%

α‐ and β‐Eliminations in Transition Metal Complexes: Strategies to Cleave Unstrained C−C and C−F Bonds

Karimzadeh

Wendt

2021

Helvetica Chimica Acta

View full text Add to dashboard Cite

Oxidative addition is the standard process for single‐bond activation in transition metal catalysis and it is known to operate for many types of bonds, but challenging σ‐bonds e. g. C(sp3)−F and C(sp3)−C(sp3) bonds are the exceptions in this respect. This short review aims at demonstrating how both α‐ and β‐eliminations may be better options for activation of unstrained C−F and C−C single bonds. Selected examples of such eliminations are presented with a mechanistic focus indicating how unstrained and unactivated C−C and C−F bonds can be broken by employing α‐ and β‐eliminations in transition metal hydrocarbyl ligands. Our examples show that the reaction barrier in β‐eliminations is controlled by the s‐character of the participating bonds where a higher s‐character gives a better overlap in the multi‐center transition state thereby increasing the reactivity; still β‐aryl eliminations can compete with the classical β‐hydrogen eliminations in certain cases.

show abstract

Section: β‐Eliminations Cleaving C−c Bondsmentioning

confidence: 99%

α‐ and β‐Eliminations in Transition Metal Complexes: Strategies to Cleave Unstrained C−C and C−F Bonds

Karimzadeh

Wendt

2021

Helvetica Chimica Acta

View full text Add to dashboard Cite

show abstract

“…Our group is interested in the study of cascade reactions involving the intramolecular carbopalladation of alkenes . Noteworthy, carbopalladation cascade reactions are not limited to the use of alkenes, they have also been successfully implemented in substrates bearing alkynyl fragments .…”

Section: Figurementioning

confidence: 99%

“…We reported recently a ligand‐controlled Pd‐catalyzed reaction taking place on 2‐haloarylethers bearing a 1,4‐diene tethered chain . We found that bulky monodentate ligands such as PCy 3 promoted a sequential double carbopalladation of the 1,4‐diene moiety, affording interesting [3.4]‐spirodihydrofuranes.…”

Section: Figurementioning

confidence: 99%

“…The increase of the Pd(OAc) 2 loading to 5 mol% afforded nearly full conversion of 1 a into the desired spirocyclic product 2 a . We tested different mono‐ and bidentate phosphine ligands (entries 8–9, Table ) to check any possible effect on the outcome of the catalytic process, as observed previously for related ether derivatives . Nevertheless, in this occasion the reaction proved insensitive to the use of different phosphines, producing the spirocycle 2 a in all the cases.…”

Section: Figurementioning

confidence: 99%

See 1 more Smart Citation

Synthesis of [3.4]‐Spirooxindoles through Cascade Carbopalladation of Skipped Dienes

et al. 2020

Self Cite

View full text Add to dashboard Cite

A synthetic route to [3.4]-spirooxindoles based on cascade carbopalladation reactions of 1,4dienes is described. While carbopalladation of alkenes have been used to access mainly [4.4]-or [4.5]-spirocycles, 4-exo-trig carbopalladation has not been yet applied to the synthesis of relevant [3.4]-spirooxindole scaffolds bearing a cyclobutyl ring. In addition, the cascade reaction generates an exocyclic double bond that can serve as a platform to further diversify the substitution pattern of the spirooxindole nuclei.

show abstract

“…It is worth to mentioning that 4-exo-trig cyclization is rarely reported (Scheme 3). [10] The fully intramolecular double Heck cyclization has also been shown to be a powerful tool for the total synthesis of natural products containing congested quaternary carbon centers.…”

Section: Fully Intramolecular Double Heck Reactionmentioning

confidence: 99%

Recent Progress in the Consecutive Double Heck Reaction

Kong

2020

Asian J Org Chem

View full text Add to dashboard Cite

Group website: http://wqkong.whu.edu.cnAlthough the Heck reaction has been discovered for more than 50 years, there remains significant opportunities for chemists to make new discoveries. The traditional Heck reaction is mainly limited to the arylation of alkenes, but the efficient construction of diverse polycyclic scaffolds bearing an alkenyl functional group in one‐pot operation by consecutive double Heck cyclization has been scarcely investigated. We therefore summarise the recent progress in Pd‐ and Ni‐catalyzed consecutive double Heck cyclization and highlight the enantioselective transformations and their applications in the total synthesis of natural products with congested quaternary carbon stereocenters.

show abstract

Pd-catalyzed cascade reactions involving skipped dienes: from double carbopalladation to remote C–C cleavage

Abstract: A ligand-controlled Pd-catalyzed cascade relying in the control of two distinctive processes: oxidative addition to Pd(0) and isomerization of olefins.

Cited by 13 publications

References 57 publications

α‐ and β‐Eliminations in Transition Metal Complexes: Strategies to Cleave Unstrained C−C and C−F Bonds

α‐ and β‐Eliminations in Transition Metal Complexes: Strategies to Cleave Unstrained C−C and C−F Bonds

Synthesis of [3.4]‐Spirooxindoles through Cascade Carbopalladation of Skipped Dienes

Recent Progress in the Consecutive Double Heck Reaction

Contact Info

Product

Resources

About