Enantioselective Synthesis of Aryl Sulfoxides via Palladium-Catalyzed Arylation of Sulfenate Anions

Maitro, Guillaume; Vogel, Sophie; Sadaoui, Mounel; Prestat, Guillaume; Madec, David; Poli, Giovanni

doi:10.1021/ol702343g

Cited by 97 publications

(50 citation statements)

References 31 publications

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“…The sulfenate anions are generated in situ by base-induced elimination of b-sulfinylesters [136]. These groups subsequently developed an enantioselective variant, allowing the asymmetric synthesis of sulfoxides with up to 83% ee (16) [105]. Chiral sulfoxides are present in a variety of pharmaceuticals and are widely used in asymmetric catalysis [137][138][139][140][141].…”

Section: Sulfenates and Sulfinatesmentioning

confidence: 99%

“…Cross-coupling of sulfinyl esters and iodoarenes with Pd(0) [105] Sulfinate anions have been used as nucleophiles in palladium-catalyzed allylic alkylation [143]. More recently, both Cu-and Pd-catalyzed couplings of sulfinate anions with aryl halides have also been reported as a means to generate unsymmetrical diaryl sulfones, which are common motifs in bioactive molecules [38,93,[144][145][146][147][148].…”

Section: Equation 16mentioning

confidence: 99%

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Organometallic Approaches to Carbon–Sulfur Bond Formation

2010

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Section: Sulfenates and Sulfinatesmentioning

confidence: 99%

Section: Equation 16mentioning

confidence: 99%

Organometallic Approaches to Carbon–Sulfur Bond Formation

2010

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“…Poli, Madec and co-workers recently disclosed a method for direct sulfoxide formation involving a Pd-catalyzed allylation or arylation of an intermediate sulfenate anion. [5] This strategy is illustrated by the reaction between tertbutyl 3-p-tolylsulfinylpropionate and cinnamyl acetate, which gave the cinnamyl p-tolyl sulfoxide. In this reaction, the sulfenate anion and h 3 -allyl complex are generated in situ and react with each other to afford the final product.…”

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confidence: 99%

Palladium‐Catalyzed Allylic Sulfinylation and the Mislow–Braverman–Evans Rearrangement

Kleimark

Prestat

Poli

et al. 2011

Chemistry A European J

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Sulfoxides play important roles in organic and medicinal chemistry, as chiral handles, [1] ligands, [2] or bioisosteres.[3]The most common method for sulfoxide preparation is controlled sulfide oxidation, [4] but a more convergent approach would be to make them by formation of the C À S bond. Poli, Madec and co-workers recently disclosed a method for direct sulfoxide formation involving a Pd-catalyzed allylation or arylation of an intermediate sulfenate anion. [5] This strategy is illustrated by the reaction between tertbutyl 3-p-tolylsulfinylpropionate and cinnamyl acetate, which gave the cinnamyl p-tolyl sulfoxide. In this reaction, the sulfenate anion and h 3 -allyl complex are generated in situ and react with each other to afford the final product. Herein, we disclose our theoretical results for the formation of the allyl sulfoxides (Scheme 1).A simplified mechanistic scheme for the formation of phenyl allyl sulfoxide is shown in Scheme 2. Sulfenate anion and h 3 -allyl Pd complexes are formed in situ and react by nucleophilic displacement. However, it is not a priori clear whether initial attack occurs from the formally anionic oxygen atom or the formally neutral sulfur atom. The observed product is the allyl sulfoxide, but this would be expected to be formed also from a rapid Mislow-BravermanEvans (MBE) rearrangement [6] even if the allyl sulfenate would be the initially formed product. Since the two mechanisms are closely linked, we initiated our investigation by a detailed computational study of the MBE rearrangement. Our standard workhorse for computational investigations of reaction mechanisms is DFT at the B3LYP level [7] with a polarized double-z basis set (6-31G*), augmented by vibrational corrections, ECP basis sets for heavy elements, [8] continuum solvation, [9] and dispersion corrections.[10] However, Jorgensen and co-workers showed that even though trends in the MBE rearrangement kinetics could be well reproduced by similar methods, the equilibrium was erroneously calculated to favor the sulfenate product, not the sulfoxide.[11] We could verify that the same problem exists also when applying our standard methods to methyl allyl sulfoxide. The correct preference for the sulfoxide could only be reproduced by using large basis sets. The results seemed reasonably well converged at the cc-PVDZ level, but due to a slight shift in energy when going to the cc-PVTZ basis [12] we selected the latter basis set for further studies. Geometries were well converged already at the 6-31G* level, as evidenced by small differences in energy between cc-PVTZ and cc-PVTZ//6-31G* calculations. Single-point cc-PVTZ calculations at 6-31G*-derived IRC points also revealed that the transition state of the rearrangement shifted by less than 0.1 with the larger basis set. Details of these investigations can be found in the Supporting Information. In conclusion, to ensure proper energetics in our studies of the Pd-catalyzed process, we performed geometry optimizations at the B3LYP level with the lacvp* basis set, [8] val...

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“…[5f, 6] More recently,t he palladium-catalyzed arylation of sulfinates generated in situ has been reported, [7] but it hasb een mostly limited to the synthesis of diaryl sulfoxides [8] with only one asymmetricv ariant described so far. [9] The synthesis of enantioenriched phosphorous compounds uses ab roader rangeo fm ethods, including the versatile hydrophosphonylationr eactions. [10] However,m ethods to generate aP -stereogenic centre are far lessc ommon.…”

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confidence: 99%

Noncovalent Substrate‐Directed Enantioselective Heck Reactions: Synthesis of S‐ and P‐Stereogenic Heterocycles

Azambuja

Carmona

Chorro

et al. 2016

Chemistry A European J

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S- and P-Stereogenic heterocycles were synthesized by a remarkably simple enantioselective Heck desymmetrization reaction based on the unprecedented noncovalent directing effect of S=O and P=O functionalities. Selected prochiral symmetric substrates were efficiently arylated using the recently disclosed chiral PyraBOx ligand under mild and open-flask reaction conditions. Several five-membered aryl- sulfones, sulfoxides, and phosphine oxides were synthesized in good to excellent yields, in good to high diastereoselectivity, and enantiomeric ratios up to 98:2. Theoretical calculations also support the noncovalent directing effect of the S=O and P=O functionalities during the arylation process.

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Enantioselective Synthesis of Aryl Sulfoxides via Palladium-Catalyzed Arylation of Sulfenate Anions

Cited by 97 publications

References 31 publications

Organometallic Approaches to Carbon–Sulfur Bond Formation

Organometallic Approaches to Carbon–Sulfur Bond Formation

Palladium‐Catalyzed Allylic Sulfinylation and the Mislow–Braverman–Evans Rearrangement

Noncovalent Substrate‐Directed Enantioselective Heck Reactions: Synthesis of S‐ and P‐Stereogenic Heterocycles

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