P-Chiral Monophosphorus Ligands for Asymmetric Copper-Catalyzed Allylic Alkylation

Xiong, Wenrui; Xu, G. S.; Yu, Xinhong; Tang, Wenjun

doi:10.1021/acs.organomet.9b00194

Cited by 20 publications

(14 citation statements)

References 92 publications

(31 reference statements)

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“…The groups of Yu and Tang demonstrated that the P-chiral monophosphorus ligand 31 facilitates the alkylation of a broad series of trisubstituted allyl bromides 32a−k (Scheme 16). 62 Moderate yields with good selectivities were achieved with para-or meta-substituted cinnamyl bromides, whereas a significantly diminished result was observed for the orthosubstituted substrate 32e (33e: 54% yield, 22% ee). In addition, the alkyl substituent at the γ-position (R) was limited to a methyl group as a n-propyl or isopropyl group led to the generation of products in low regio-and enantioselectivity (33j and 33k).…”

Section: Catalytic Enantioselective Allylic Alkylation Withcontrasting

confidence: 99%

Enantioselective Formation of Quaternary Centers by Allylic Alkylation with First-Row Transition-Metal Catalysts

2021

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Asymmetric allylic alkylation mediated by transition metals provides an efficient strategy to form quaternary stereogenic centers. While this transformation is dominated by the use of second- and third-row transition metals (e.g., Pd, Rh, and Ir), recent developments have revealed the potential of first-row transition metals, which provide not only a less expensive and potentially equally efficient alternative but also new mechanistic possibilities. This review summarizes examples for the assembly of quaternary stereocenters using prochiral allylic substrates and hard, achiral nucleophiles in the presence of copper complexes and highlights the complementary approaches with soft, prochiral nucleophiles catalyzed by chiral cobalt and nickel complexes.

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Section: Catalytic Enantioselective Allylic Alkylation Withcontrasting

confidence: 99%

Enantioselective Formation of Quaternary Centers by Allylic Alkylation with First-Row Transition-Metal Catalysts

2021

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“…Following representative procedure E, ( E )-3-(4-chlorophenyl)prop-2-en-1-ol (1.08 g 6.4 mmol) was brominated to afford 1.31 g (89%) of E2 as a pale-yellow oil. Spectroscopic data for E2 matched reported literature values and was used without further purification.…”

Section: Methodsmentioning

confidence: 88%

Synthesis of Enantioenriched 3,4-Disubstituted Chromans through Lewis Base Catalyzed Carbosulfenylation

2021

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A method for the catalytic, enantioselective, carbosulfenylation of alkenes to construct 3,4-disubstituted chromans is described. Alkene activation proceeds through the intermediacy of enantioenriched, configurationally stable thiiranium ions generated from catalytic, Lewis base activation of an electrophilic sulfenylating agent. The transformation affords difficult-to-generate, enantioenriched, 3,4-disubstituted chromans in moderate to high yields and excellent enantioselectivities. A variety of substituents are compatible including electronically diverse functional groups as well as several functional handles such as aryl halides, esters, anilines, and phenols. The resulting thioether moiety is amenable to a number of functional group manipulations and transformations. Notably, the pendant sulfide was successfully cleaved to furnish a free thiol which readily provides access to most sulfur-containing functional groups which are present in natural products and pharmaceuticals.

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“…BI‐DIME provided the cyclization product 2 a in 78 % yield. More sterically hindered ligand L3 was more effective, leading to the formation of 2 a in 82 % yield. Ligands L4 and L5 with substituents at the 3,5‐positions provided even higher yields.…”

Section: Figurementioning

confidence: 99%

Construction of Various Bridged Polycyclic Skeletons by Palladium‐Catalyzed Dearomatization

Peng

et al. 2020

Angew Chem Int Ed

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A powerful palladium‐catalyzed dearomative cyclization was developed that provides facile access to eight types of bridged tetracyclic skeletons bearing various ring sizes and heterocycles. With this method, several skeletons or analogues of natural products, including tubingensin B and dracaenones, were synthesized. Asymmetric dearomative cyclization enables the construction of various enantiomerically enriched bridged polycyclic systems with up to 99 % ee by employing a chiral palladium catalyst.

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P-Chiral Monophosphorus Ligands for Asymmetric Copper-Catalyzed Allylic Alkylation

Cited by 20 publications

References 92 publications

Enantioselective Formation of Quaternary Centers by Allylic Alkylation with First-Row Transition-Metal Catalysts

Enantioselective Formation of Quaternary Centers by Allylic Alkylation with First-Row Transition-Metal Catalysts

Synthesis of Enantioenriched 3,4-Disubstituted Chromans through Lewis Base Catalyzed Carbosulfenylation

Construction of Various Bridged Polycyclic Skeletons by Palladium‐Catalyzed Dearomatization

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