Enantioselective α‐Allylation of Acyclic Esters Using B(pin)‐Substituted Electrophiles: Independent Regulation of Stereocontrol Elements through Cooperative Pd/Lewis Base Catalysis

Scaggs, William R.; Snaddon, Thomas N.

doi:10.1002/chem.201803543

Cited by 40 publications

(9 citation statements)

References 54 publications

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“… 403 − 405 Various aryl- and vinyl acetic acid esters were α-allylated with Bpin-substituted allyl mesylates ( ee values up to 96%; Scheme 125 a). 403 Pyrrolyl-acetic esters were also α-allylated with a range of allyl sulfonates or carbonates with high levels of enantioselectivity ( Scheme 125 b). 404 This allylation method was also combined with a subsequent Hofmann rearrangement in a one-pot procedure.…”

Section: Asymmetric Allylic Substitutionmentioning

confidence: 99%

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

Pàmies

Margalef

Cañellas³

et al. 2021

Chem. Rev.

371

202

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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.

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Section: Asymmetric Allylic Substitutionmentioning

confidence: 99%

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

Pàmies

Margalef

Cañellas³

et al. 2021

Chem. Rev.

371

202

View full text Add to dashboard Cite

show abstract

“…Employing Pd 2 dba 3 and bidentate ( S )‐BINAP catalyst‐ligand system in combination with ( S )‐BTM was found to be optimal for the addition of enolates to B(pin)‐substituted allylic mesylate electrophiles [74] . Notably, mismatched effects were observed when ( R )‐BINAP was used with ( S )‐BTM, where the enantioselectivity slightly decreased in this case.…”

Section: Catalyst Turnover Via Aryloxidementioning

confidence: 95%

Generation and Reactivity of C(1)‐Ammonium Enolates by Using Isothiourea Catalysis

McLaughlin

Smith

2020

Chemistry A European J

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C(1)‐Ammonium enolates are powerful, catalytically generated synthetic intermediates applied in the enantioselective α‐functionalisation of carboxylic acid derivatives. This minireview describes the recent developments in the generation and application of C(1)‐ammonium enolates from various precursors (carboxylic acids, anhydrides, acyl imidazoles, aryl esters, α‐diazoketones, alkyl halides) using isothiourea Lewis base organocatalysts. Their synthetic utility in intra‐ and intermolecular enantioselective C−C and C−X bond forming processes on reaction with various electrophiles will be showcased utilising two distinct catalyst turnover approaches.

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“…Our initial investigation was focused on a palladium‐catalyzed three‐component reaction involving benzaldehyde 1 a , γ‐borylated allyl benzoate 2 a as a bifunctional conjunctive reagent, [16] and (triisopropylsilyl)ethynyltributylstannane 3 a (Table 1).…”

Section: Methodsmentioning

confidence: 99%

Palladium‐Catalyzed Diastereoselective Synthesis of (Z)‐Conjugated Enynyl Homoallylic Alcohols

et al. 2021

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The diastereoselective synthesis of antihomoallylic alcohols bearing conjugated (Z)-enynes through a palladium-catalyzed three-component reaction is described. This reaction features a broad substrate scope, good functional group compatibility, and high levels of (Z)-alkene stereocontrol. In this reaction, Pd(0) functions as a catalyst in two fundamental steps of the tandem sequence: 1) the generation of a borylated π-allylpalladium species from bifunctional conjunctive reagents, inducing umpolung allylation of aldehydes, and 2) C(sp 2 )À C-(sp) cross-coupling. Further transformations of the obtained products highlight their synthetic utility.

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Enantioselective α‐Allylation of Acyclic Esters Using B(pin)‐Substituted Electrophiles: Independent Regulation of Stereocontrol Elements through Cooperative Pd/Lewis Base Catalysis

Cited by 40 publications

References 54 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

Generation and Reactivity of C(1)‐Ammonium Enolates by Using Isothiourea Catalysis

Palladium‐Catalyzed Diastereoselective Synthesis of (Z)‐Conjugated Enynyl Homoallylic Alcohols

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