Palladium‐Catalyzed Stereoselective Cleavage of C−P Bond: Enantioselective Construction of Atropisomers Containing a P‐Stereogenic Center

Pang, Liangzhi; Sun, Qilin; Huang, Zhan; Li, Gen; Liu, Jiaojiao; Guo, Jiaxu; Yao, Chuan‐Zhi; Yu, Jie; Li, Qiankun

doi:10.1002/ange.202211710

“…In their following studies, the same group extended their protocol to the catalytic asymmetric synthesis of other biaryl atropisomers containing a P-stereogenic center with a range of coupling partners, such as alkynes 212, R 3 Si-Bpin 214, diboron esters 216, and hydride source (H 2 O/B 2 pin 2 ), affording various enantioenriched structurally diverse chiral monodentate biaryl phosphines with excellent diastereoand enantioselectivities (Scheme 48a). [96] These chiral monodentate biaryl phosphines could be directly used as chiral catalysts in asymmetric (3 + 2) annulation of MBH carbonate with N-methylmaleimide to give chiral functionalized bicyclic imide with excellent diastereo-and enantioselectivities. These results indicated the great potential of this class of chiral biaryl phosphines in the development of valuable chiral ligands and organocatalysts (Scheme 48b).…”

Section: Atropisomers With P-stereogenic Centersmentioning

confidence: 99%

Catalytic Asymmetric Synthesis of Atropisomers Bearing Multiple Chiral Elements: An Emerging Field

Zhang,

Li,

Liu

et al. 2023

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With the rapid development of asymmetric catalysis, the demand for the enantioselective synthesis of complex and diverse molecules with different chiral elements is increasing. Owing to the unique features of atropisomerism, the catalytic asymmetric synthesis of atropisomers has attracted a considerable interest from the chemical science community. In particular, introducing additional chiral elements, such as carbon center chirality, heteroatomic chirality, planar chirality, and helical chirality, into atropisomers provides an opportunity to incorporate new properties into axially chiral compounds, thus expanding the potential applications of atropisomers. Thus, it is important to perform catalytic asymmetric transformations to synthesize atropisomers bearing multiple chiral elements. In spite of challenges in such transformations, in recent years, chemists have devised powerful strategies under asymmetric organocatalysis or metal catalysis, synthesizing a wide range of enantioenriched atropisomers bearing multiple chiral elements. Therefore, the catalytic asymmetric synthesis of atropisomers bearing multiple chiral elements has become an emerging field. This minireview summarizes the rapid progress in this field and indicates challenges, thereby promoting this field to a new horizon.

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“…The final strategy is an enantioselective desymmetrization by which prochiral groups linked to a phosphorus center are differentiated by a chiral catalyst (Scheme 1B, v). Multiple reactions have been developed using this strategy, however, until recently, none have involved chemistry occurring at the P atom directly, but rather generate the P stereocenter indirectly (through manipulation of enantiotopic side chains) inherently limiting their applicability [45–77] …”

Section: Introductionmentioning

confidence: 99%

Second Generation Catalytic Enantioselective Nucleophilic Desymmetrization at Phosphorus (V): Improved Generality, Efficiency and Modularity

Formica,

Ferko,

Marsh

et al. 2024

Angewandte Chemie

0

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A broadly improved second generation catalytic two‐phase strategy for the enantioselective synthesis of chiral at phosphorus (V) compounds is described. This protocol, consisting of a bifunctional iminophosphorane (BIMP) catalyzed nucleophilic desymmetrization of prochiral, bench stable P(V) precursors and subsequent enantiospecific substitution allows for divergent access to a wide range of C‐, N‐, O‐ and S‐ substituted P(V) containing compounds from a handful of enantioenriched precursors. A new ureidopeptide BIMP catalyst/thiaziolidinone leaving group combination allowed for a far wider substrate scope and increased reaction efficiency and practicality over previously established protocols. The resulting enantioenriched intermediates could then be transformed into an even greater range of distinct classes of P(V) compounds by displacement of the remaining leaving group as well as allowing for even further diversification downstream. Density functional theory (DFT) calculations were performed to pinpoint the origin of enantioselectivity for the BIMP‐catalyzed desymmetrization, to rationalize how a superior catalyst/leaving group combination leads to increased generality in our second‐generation catalytic system, as well as to shed light onto observed retention and inversion pathways when performing late‐stage enantiospecific SN2@P reactions with Grignard reagents.

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“…The final strategy is an enantioselective desymmetrization by which prochiral groups linked to a phosphorus center are differentiated by a chiral catalyst (Scheme 1B, v). Multiple reactions have been developed using this strategy, however, until recently, none have involved chemistry occurring at the P atom directly, but rather generate the P stereocenter indirectly (through manipulation of enantiotopic side chains) inherently limiting their applicability [45–77] …”

Section: Introductionmentioning

confidence: 99%

Second Generation Catalytic Enantioselective Nucleophilic Desymmetrization at Phosphorus (V): Improved Generality, Efficiency and Modularity

Formica,

Ferko,

Marsh

et al. 2024

Angew Chem Int Ed

9

0

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A broadly improved second generation catalytic two‐phase strategy for the enantioselective synthesis of chiral at phosphorus (V) compounds is described. This protocol, consisting of a bifunctional iminophosphorane (BIMP) catalyzed nucleophilic desymmetrization of prochiral, bench stable P(V) precursors and subsequent enantiospecific substitution allows for divergent access to a wide range of C‐, N‐, O‐ and S‐ substituted P(V) containing compounds from a handful of enantioenriched precursors. A new ureidopeptide BIMP catalyst/thiaziolidinone leaving group combination allowed for a far wider substrate scope and increased reaction efficiency and practicality over previously established protocols. The resulting enantioenriched intermediates could then be transformed into an even greater range of distinct classes of P(V) compounds by displacement of the remaining leaving group as well as allowing for even further diversification downstream. Density functional theory (DFT) calculations were performed to pinpoint the origin of enantioselectivity for the BIMP‐catalyzed desymmetrization, to rationalize how a superior catalyst/leaving group combination leads to increased generality in our second‐generation catalytic system, as well as to shed light onto observed retention and inversion pathways when performing late‐stage enantiospecific SN2@P reactions with Grignard reagents.

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Palladium‐Catalyzed Stereoselective Cleavage of C−P Bond: Enantioselective Construction of Atropisomers Containing a P‐Stereogenic Center

Cited by 7 publications

References 144 publications

Catalytic Asymmetric Synthesis of Atropisomers Bearing Multiple Chiral Elements: An Emerging Field

Catalytic Asymmetric Synthesis of Atropisomers Bearing Multiple Chiral Elements: An Emerging Field

Second Generation Catalytic Enantioselective Nucleophilic Desymmetrization at Phosphorus (V): Improved Generality, Efficiency and Modularity

Second Generation Catalytic Enantioselective Nucleophilic Desymmetrization at Phosphorus (V): Improved Generality, Efficiency and Modularity

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