Kinetic Resolution of Racemic Allylic Alcohols by Catalytic Asymmetric Substitution of the OH Group with Monosubstituted Hydrazines

Yan, L.; Xu, Jian; Huang, Chaofan; He, Zeng-Yang; Xu, Yanan; Tian, Shi‐Kai

doi:10.1002/chem.201601747

Cited by 25 publications

(18 citation statements)

References 121 publications

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“…An asymmetric allylic alkylation using an acetone nucleophile generated a chiral allylic compound was reported by Zhang et al . Recently, Tian also reported a kinetic resolution of racemic allylic alcohols through a palladium/sulfonyl‐hydrazide‐catalyzed enantioselective allylation . Asymmetric Tsuji–Trost type reaction catalyzed by Ir, Ru, and other metals has also been reported, by mainly Carreira .…”

Section: Introductionmentioning

confidence: 92%

Tsuji–Trost Reaction of Non‐Derivatized Allylic Alcohols

Akkarasamiyo

Sawadjoon

Orthaber

et al. 2018

Chemistry A European J

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Palladium-catalyzed allylic substitution of non-derivatized enantioenriched allylic alcohols with a variety of uncharged N-, S-, C- and O-centered nucleophiles using a bidentate BiPhePhos ligand is described. A remarkable effect of the counter ion (X) of the XPd[κ -BiPhePhos][η -C H ] was observed. When ClPd[κ -BiPhePhos][η -C H ] (complex I) was used as catalyst, non-reproducible results were obtained. Study of the complex by X-ray crystallography, P NMR spectroscopy, and ESI-MS showed that a decomposition occurred where one of the phosphite ligands was oxidized to the corresponding phosphate, generating ClPd[κ -BiPhePhosphite-phosphate][η -C H ] species (complex II). When the chloride was exchanged to the weaker coordinating OTf counter ion the more stable Pd[κ -BiPhePhos][η -C H ] +[OTf] (complex III) was formed. Complex III performed better and gave higher enantiospecificities in the substitution reactions. Complex III was evaluated in Tsuji-Trost reactions of stereogenic non-derivatized allylic alcohols. The desired products were obtained in good to excellent yields (71-98 %) and enantiospecificities (73-99 %) for both inter- and intramolecular substitution reactions with only water generated as a by-product. The methodology was applied to key steps in total synthesis of (S)-cuspareine and (+)-lentiginosine. A reaction mechanism involving a palladium hydride as a key intermediate in the activation of the hydroxyl group is proposed in the overall transformation.

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Section: Introductionmentioning

confidence: 92%

Tsuji–Trost Reaction of Non‐Derivatized Allylic Alcohols

Akkarasamiyo

Sawadjoon

Orthaber

et al. 2018

Chemistry A European J

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“…A range of chiral allylic alcohols and allylic hydrazines was accessed in excellent selectivity values ( s values up to >400) using the Pd/( S )-SegPhos catalyst and 2,5-dichlorobenzenesulfonohydrazide 6 as additive ( Scheme 50 b). 143 …”

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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“…A reaction that proceeds through an unsymmetrical disubstituted metal−π-allyl intermediate allows for direct access to products that contain an allylic stereogenic center and a 1,2-disubstituted olefin (Scheme C). Although this type of species has been accessed in allylic substitutions from substrates such as 7 , Tsuji–Trost reactions of this type are uncommon and present a number of challenges. First, attack at C1 versus C3 leads to different product regioisomers (cf., Scheme A).…”

Section: Introductionmentioning

confidence: 99%

Catalytic Enantio- and Regioselective Addition of Nucleophiles in the Intermolecular Hydrofunctionalization of 1,3-Dienes

2019

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Catalytic enantioselective synthesis of small-molecule building blocks with allylic stereogenic centers is an important objective in organic synthesis, but preparing this motif wherein the adjacent olefin is 1,2-disubstituted in a single step is a tremendous challenge. Late-transition-metal-catalyzed intermolecular couplings of nucleophiles and 1,3-dienes in hydrofunctionalization reactions have quickly emerged as a compelling approach to these and related compounds. In this Perspective, we illustrate how these intermolecular diene hydrofunctionalizations have provided an avenue to complex, highly desirable chemical space that is not readily accessed by other technologies. We also aim to provide some insight into the varying mechanistic pathways and nuances of these myriad reactions to help inform future reaction and catalyst design.

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Kinetic Resolution of Racemic Allylic Alcohols by Catalytic Asymmetric Substitution of the OH Group with Monosubstituted Hydrazines

Cited by 25 publications

References 121 publications

Tsuji–Trost Reaction of Non‐Derivatized Allylic Alcohols

Tsuji–Trost Reaction of Non‐Derivatized Allylic Alcohols

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

Catalytic Enantio- and Regioselective Addition of Nucleophiles in the Intermolecular Hydrofunctionalization of 1,3-Dienes

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