Palladium-catalyzed asymmetric allylic alkylation of indoles by C–N bond axially chiral phosphine ligands

Mino, Takashi; Ishikawa, Miho; Nishikawa, Kenji; Wakui, Kazuya; Sakamoto, Masami

doi:10.1016/j.tetasy.2013.03.008

Cited by 52 publications

(35 citation statements)

References 33 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…270 Mino's group described another example of backbone control with the atropoisomeric 1-diphenylphosphino-2-amino ligand L83 inducing ee values of up to 95% in the allylic alkylation of rac-1,3-diphenylallyl acetate (Scheme 77). 268,282 Later on, Miller's group extended Mino's design to amides (ligand L84; ee values up to 92%, Scheme 77). 280 A second strategy to favor stereoselective coordination of the N-group relies on introducing chiral substituents at the Ngroup.…”

Section: T H Imentioning

confidence: 99%

“…In a mechanistic investigation, a near first order dependence on Pd-catalyst and NHC was found. 707 In that study, the crucial role of the phosphine ligand and a nonlinear effect of the chiral NHC organocatalyst (282) were established, prompting a search for the existence of a mixed Pd complex containing both the phosphine ligand and the chiral NHC. ESI-MS and X-ray investigations did indeed indicate the formation of a catalytically active [Pd(η 3 -allyl)(NHC)(PPh 3 )] complex.…”

Section: [4+n] Cycloaddition Reactionsmentioning

confidence: 99%

See 1 more Smart Citation

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Pàmies

Margalef

Cañellas³

et al. 2021

Chem. Rev.

369

202

View full text Add to dashboard Cite

This Review compiles the evolution, mechanistic understanding, and more recent advances in enantioselective Pd-catalyzed allylic substitution and decarboxylative and oxidative allylic substitutions. For each reaction, the catalytic data, as well as examples of their application to the synthesis of more complex molecules, are collected. Sections in which we discuss key mechanistic aspects for high selectivity and a comparison with other metals (with advantages and disadvantages) are also included. For Pd-catalyzed asymmetric allylic substitution, the catalytic data are grouped according to the type of nucleophile employed. Because of the prominent position of the use of stabilized carbon nucleophiles and heteronucleophiles, many chiral ligands have been developed. To better compare the results, they are presented grouped by ligand types. Pd-catalyzed asymmetric decarboxylative reactions are mainly promoted by PHOX or Trost ligands, which justifies organizing this section in chronological order. For asymmetric oxidative allylic substitution the results are grouped according to the type of nucleophile used.

show abstract

Section: T H Imentioning

confidence: 99%

Section: [4+n] Cycloaddition Reactionsmentioning

confidence: 99%

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Pàmies

Margalef

Cañellas³

et al. 2021

Chem. Rev.

369

202

View full text Add to dashboard Cite

show abstract

“…In another report, Mino and coworkers employed indole as a nucleophile in AAA reaction that resulted in very high enantioselectivity. 247 The same group also successfully demonstrated a resolution technique in an asymmetric allylic alkylation reaction using atropisomeric ligand 394.…”

Section: Catalysismentioning

confidence: 99%

Nonbiaryl and Heterobiaryl Atropisomers: Molecular Templates with Promise for Atropselective Chemical Transformations

et al. 2015

View full text Add to dashboard Cite

“…(S,E)-3-(1,3-diphenylallyl)-4-methyl-1H-indole ( 3d ) [17]: White solid (m.p. 172–174 °C), 93% yield.…”

Section: Methodsmentioning

confidence: 99%

“…Hoshi reported that high yields and good enantioselectivities were obtained with sulphur-MOP ligands [16]. A phosphine ligand developed by Mino afforded 89% yields and 80% enatioselectivities with narrow substrate scope [17]. Other ligands such as phosphoramidite-thioether [18], phosphoramidite-terminal olefin [19], phosphine olefin [20,21], and helicenylphosphine ligands [22] were also reported as efficient catalysts.…”

Section: Introductionmentioning

confidence: 99%

Spiro Indane-Based Phosphine-Oxazolines as Highly Efficient P,N Ligands for Enantioselective Pd-Catalyzed Allylic Alkylation of Indoles and Allylic Etherification

et al. 2019

View full text Add to dashboard Cite

A series of indane-based phosphine-oxazoline ligands with a spirocarbon stereogenic center were examined for palladium-catalyzed asymmetric allylic alkylation of indoles. Under optimized conditions, high yields (up to 98%) and enantioselectivities (up to 98% ee) were obtained with a broad scope of indole derivatives. The ligand was determined to be the most efficient P,N-ligand for this reaction. Moreover, the ligand was also efficient for Pd-catalyzed asymmetric allylic etherification with hard aliphatic alcohols as nucleophiles.

show abstract

Palladium-catalyzed asymmetric allylic alkylation of indoles by C–N bond axially chiral phosphine ligands

Cited by 52 publications

References 33 publications

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Nonbiaryl and Heterobiaryl Atropisomers: Molecular Templates with Promise for Atropselective Chemical Transformations

Spiro Indane-Based Phosphine-Oxazolines as Highly Efficient P,N Ligands for Enantioselective Pd-Catalyzed Allylic Alkylation of Indoles and Allylic Etherification

Contact Info

Product

Resources

About