Recent Advances in First-Row Transition Metal/Chiral Phosphoric Acid Combined Catalysis

Fang, Guichun; Cheng, Yuan; Yu, Zhang‐Long; Li, Zhongliang; Liu, Xin‐Yuan

doi:10.1007/s41061-019-0249-0

Cited by 25 publications

(9 citation statements)

References 141 publications

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“…It has been noted that direct trapping of benzylic radicals by NHPI and peroxide analogues catalyzed by the Cu(I)/CPA/Zn(II) combination has been reported to give their trapping adducts as side products in an almost racemic form . Further examinations of the representative, chiral phosphoric acid (CPA) L′ based on ( R , R )-2,2′-anthryl-1,1′-binol as an alternative additive to the test reactions catalyzed by V(O)(II), Fe(II), and Cu(I) led to ( S )- 2′ in 68–62% yields with 24% and 46% ees, respectively, for V(O)(II)/Fe(II) and Cu(I) (cf. entries 4/5 and 6).…”

Section: Resultsmentioning

confidence: 99%

Enantioselective Radical Type, 1,2-Oxytrifluoromethylation of Olefins Catalyzed by Chiral Vanadyl Complexes: Importance of Noncovalent Interactions

Chen

et al. 2021

ACS Catal.

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Asymmetric three-component 1,2-oxytrifluoromethylations of styrenes were explored by using N-oxyphthalimide (NOPI) as the resulting benzylic radical anchor after cross-coupling by a CF3 radical under the catalyses of chiral N-salicylidene-derived oxovanadium(V) complexes. Among the 15 different solvents and 15 different catalysts examined, the best scenarios were in i-PrOH with C3-tert-butyl or C3-fluoro-/2,5-dimethylphenyl-substituted vanadyl catalysts that led to the corresponding complementary S and R products in up to 88% yields and 87/86% ees, respectively, with further enrichment to at least 94% ee after a single recrystallization. The ccontrol α-(2-phenylcyclopropyl)styrene was tested to prove the asymmetric event involving the benzylic radical species. DFT computations showed that the SOMO of the benzylic radical is placed in a way to orient the CF3CH2 group away from the tert-butyl group in the salicylidene-l-tert-butylglycinate template by interacting with the N-oxygen atom of NOPI bound to the vanadium center with a bimolecular homolytic substitution (SH2) type mechanism. The enantioselectivity profile was dominated by several noncovalent interactions between the intermediary vanadium(NOPI) complex and the resulting benzylic radical.

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Section: Resultsmentioning

confidence: 99%

Enantioselective Radical Type, 1,2-Oxytrifluoromethylation of Olefins Catalyzed by Chiral Vanadyl Complexes: Importance of Noncovalent Interactions

Chen

et al. 2021

ACS Catal.

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“…Thus, previously inaccessible asymmetric transformations can be carried out with multiple catalysts as both metal and organocatalysts work differently. [59][60][61][62] The intelligent construction of the majority of CPAs involves tuning of substituents at the 3,3' position of the binaphthyl skeletons. Conventionally, they induce chirality by hydrogen bonding interactions with a weak basic functional group to form a contact ion pair with electrophilic components, via their relatively strong, yet appropriate, acidity.…”

Section: Combining Brønsted Acid Catalysis With Transition Metal Cata...mentioning

confidence: 99%

“…[63,64] The CPAs simultaneously having acid/ base dual functionality in combination with transition metals such as Cu, Rh, Ru, Ag, Pd, Au, Ir, Fe, Co exhibit multiple and peculiar reactivities beyond the single acid effect for asymmetric reactions (Figure 2). [60] Herein, we will discourse the advances of the last 5 years of combined phosphoric acid (both chiral as well as non-chiral) and transition metal-catalyzed chemical transformations. This includes chemical bond formation in olefin isomerization/metathesis, hydroamination/hydroalkoxylation of alkynes and enantioenriched heterocycles synthesis.…”

Section: Combining Brønsted Acid Catalysis With Transition Metal Cata...mentioning

confidence: 99%

“…The CPAs simultaneously having acid/base dual functionality in combination with transition metals such as Cu, Rh, Ru, Ag, Pd, Au, Ir, Fe, Co exhibit multiple and peculiar reactivities beyond the single acid effect for asymmetric reactions (Figure 2). [60] …”

Section: Combining Brønsted Acid Catalysis With Transition Metal Cata...mentioning

confidence: 99%

“…In recent decades, beyond the scope of typical acid catalysis, metal and chiral organocatalysts combination has emerged as a fruitful tool for asymmetric synthesis. Thus, previously inaccessible asymmetric transformations can be carried out with multiple catalysts as both metal and organocatalysts work differently [59–62] …”

Section: Combining Brønsted Acid Catalysis With Transition Metal Cata...mentioning

confidence: 99%

See 2 more Smart Citations

Combined Power of Organo‐ and Transition Metal Catalysis in Organic Synthesis

et al. 2022

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The combination of organocatalysis with transition metal catalysis is an emerging research area for the scientific community. Various unprecedented transformations that are otherwise inaccessible by individual catalytic systems can be achieved with good efficiency and stereocontrolled manner by this dual-catalytic strategy. This Review presents a detailed discussion on the recent advances in dual catalytic systems combining organocatalysis and transition metal catalysis, covering the literature of the last five years. A wide variety of combinations of transition metals with organocatalysts including aminocatalysts, such as secondary amines and more recent primary amines, Brønsted acid catalysts, especially phosphoric acids based on the chiral BINOL scaffold and N-heterocyclic carbene catalysts, are discussed. Considering the great contribution of this domain to organic synthesis, the present and future potential of this new and exciting research field is highlighted.

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Asymmetric Alkynylation of Cyclic N‐Sulfonyl Imines using Synergistic Chiral Phosphoric Acid/Copper Catalysis

Liu

Chen

et al. 2020

Adv Synth Catal

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The catalytic enantioselective alkynylation of six‐membered cyclic N‐sulfonyl imines was achieved using a cooperative chiral phosphoric acid and Cu(I) catalyst. This alkynylation reaction displays a broad substrate scope for both terminal alkynes and benzoxathiazine 2,2‐dioxides and provides a highly efficient method for the synthesis of chiral propargylic sulfamidates in up to 95% yield and 99% enantiomeric excess.magnified image

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Recent Advances in First-Row Transition Metal/Chiral Phosphoric Acid Combined Catalysis

Cited by 25 publications

References 141 publications

Enantioselective Radical Type, 1,2-Oxytrifluoromethylation of Olefins Catalyzed by Chiral Vanadyl Complexes: Importance of Noncovalent Interactions

Enantioselective Radical Type, 1,2-Oxytrifluoromethylation of Olefins Catalyzed by Chiral Vanadyl Complexes: Importance of Noncovalent Interactions

Combined Power of Organo‐ and Transition Metal Catalysis in Organic Synthesis

Asymmetric Alkynylation of Cyclic N‐Sulfonyl Imines using Synergistic Chiral Phosphoric Acid/Copper Catalysis

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