Desymmetrization of Phosphinic Acids via Pd-Catalyzed Asymmetric Allylic Alkylation: Rapid Access to <i>P</i>-Chiral Phosphinates

Trost, Barry M.; Spohr, Simon M.; Rolka, Alessa; Kalnmals, Christopher A.

doi:10.1021/jacs.9b07340

Cited by 59 publications

(23 citation statements)

References 46 publications

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“…Trost’s group has also reported an efficient desymmetrization of phosphinic acids with an interesting modification of the Trost ligand, the ( S,S )-diaminoethanoanthracene-based ligand L23 ( Scheme 26 ). 101 The Pd/( S,S )- L23 catalyst was able to discriminate between the two enantiotopic oxygen atoms providing a novel synthetic path to P -chiral phosphinates with high diastereo- and enantioselectivities ( Scheme 26 ).…”

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.

407

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.

407

202

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“…12 In 2019, Trost showed the desymmetrization of phosphinic acids by stereoselectively alkylating one of the enantiotopic oxygens through Pd-catalyzed asymmetric allylic alkylation to give P-stereogenic phosphinates with diversied substituents (Scheme 1, eqn (2b)). 13 Therefore, it is desirable to develop other new methods for the synthesis of multifunctional P-stereogenic phosphinates.…”

Section: Introductionmentioning

confidence: 99%

Palladium-catalyzed asymmetric hydrophosphorylation of alkynes: facile access to P-stereogenic phosphinates

Yang

Han

et al. 2020

Chem. Sci.

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“… 23 The racemic alkyl-aryl secondary phosphine oxides ( 1j – n ) were prepared according to a literature procedure by reacting PhPCl 2 with ethanol and treating the in situ formed ethyl phenyl- H -phosphinate with the corresponding organometallic reagent. 12b , 24 …”

Section: Resultsmentioning

confidence: 99%

Enantioseparation of P-Stereogenic Secondary Phosphine Oxides and Their Stereospecific Transformation to Various Tertiary Phosphine Oxides and a Thiophosphinate

et al. 2021

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Secondary phosphine oxides incorporating various aryl and alkyl groups were synthesized in racemic form, and these products formed the library reported in this study. TADDOL derivatives were used to obtain the optical resolution of these P -stereogenic secondary phosphine oxides. The developed resolution method showed a good scope under the optimized reaction conditions, as 9 out of 14 derivatives could be prepared with an enantiomeric excess (ee) ≥ 79% and 5 of these derivatives were practically enantiopure >P(O)H compounds (ee ≥ 98%). The scalability of this resolution method was also demonstrated. Noncovalent interactions responsible for the formation of diasteromeric complexes were elucidated by single-crystal XRD measurements. ( S )-(2-Methylphenyl)phenylphosphine oxide was transformed to a variety of P -stereogenic tertiary phosphine oxides and a thiophosphinate in stereospecific Michaelis–Becker, Hirao, or Pudovik reactions.

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Desymmetrization of Phosphinic Acids via Pd-Catalyzed Asymmetric Allylic Alkylation: Rapid Access to P-Chiral Phosphinates

Cited by 59 publications

References 46 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

Palladium-catalyzed asymmetric hydrophosphorylation of alkynes: facile access to P-stereogenic phosphinates

Enantioseparation of P-Stereogenic Secondary Phosphine Oxides and Their Stereospecific Transformation to Various Tertiary Phosphine Oxides and a Thiophosphinate

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