Enantioselective Synthesis of Planar-Chiral Phosphines with 1,N-Dioxa[N]paracyclophane Scaffold and Their Application as Chiral Ligands

Kanda, Kazumasa; Oshima, Shoya; Shizuno, Tsubasa; Hamanaka, Risa; Fukai, Miku; Shibata, Takanori

doi:10.3987/com-13-s(s)105

Cited by 13 publications

(1 citation statement)

References 53 publications

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“…A representative planar chiral structure is a medium-ring or macrocyclic cyclophane comprising an arene and a bridging chain connected to two points on the arene . While planar chiral macrocyclic paracyclophanes are now accessible by biocatalytic, organocatalytic, transition-metal-catalyzed, and stoichiometric lithiation methods, examples of catalytic, enantioselective synthesis of chiral macrocyclic metacyclophanes remain sparse. − Despite the potential generality of enantioselective macrocyclization reactions where bond formation occurs at the prochiral plane to access planar chiral cyclophanes, there are only two known examples applied to the synthesis of metacyclophanes. Beaudry and co-workers reported the synthesis of enantioenriched planar chiral metacyclophanes related to diarylether heptanoid natural products by enantioselective macrocyclization by Ullman coupling (Scheme A) .…”

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Enantioselective Synthesis of Planar Chiral Macrocyclic Metacyclophanes by Pd-Catalyzed C–O Cross-Coupling

Wei

Chen

2023

ACS Catal.

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Despite the presence of planar chiral elements in natural products and in ligands for asymmetric catalysis, catalytic enantioselective methods for installing planar chirality remain underdeveloped relative to methods for installing central and axial chirality. Here, we report an enantioselective Pd-catalyzed C–O bond-forming macrocyclization to access enantioenriched planar chiral macrocyclic metacyclophanes incorporating 2,3,4-trisubstituted pyridines. A variety of bridging chains and substituents can be incorporated in the metacyclophanes under the same reaction conditions (14 examples, 59–85% yields, 79–92% ee) to generate enantioenriched meta-, metaortho-, and metapara- cyclophanes. The syn-/anti-conformational preferences of metacyclophanes were elucidated by the X-ray structures, 1H NMR analyses, and computational studies. We also found that the two enantiomers of the metacyclophane can be obtained using the same enantiomer of the chiral ligand by starting from two regioisomeric linear precursors. This work provides an entry into the design of enantioselective cross-coupling macrocyclizations to access planar chiral structures for applications in medicinal chemistry and catalysis.

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confidence: 99%

Enantioselective Synthesis of Planar Chiral Macrocyclic Metacyclophanes by Pd-Catalyzed C–O Cross-Coupling

Wei

Chen

2023

ACS Catal.

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Asymmetric Synthesis of Planar Chiral and Helically Chiral Compounds

Shibata

2022

Catalytic Asymmetric Synthesis

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Atroposelective Synthesis of Planar‐Chiral Indoles via Carbene Catalyzed Macrocyclization

Yang,

He,

Wang

et al. 2023

Angewandte Chemie

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Indole‐based planar‐chiral macrocycles are widely found in natural products and bioactive molecules. However, in sharp contrast to the preparation of indole‐based axially chiral structures, the enantioselective catalysis of indole‐based planar‐chiral macrocycles is still a formidable task so far. Here we report an N‐heterocyclic carbene (NHC)‐catalyzed intramolecular atroposelective macrocyclization of 3‐carboxaldehyde indole/pyrroles, featuring with broad substrate scope and good functional group tolerance, and allowing for a rapid access to diverse indole/pyrrole‐based planar‐chiral macrocycles with various tether‐lengths (10–16 members) in good yields and with excellent enantioselectivities. Importantly, the indole‐based macrocyclic structures with both planar and axial chirality were directly and efficiently obtained through this protocol with excellent enantioselectivities and diastereoselectivities. In addition, these synthesized planar‐chiral macrocycles offer many possibilities for chemists to develop new catalysts or ligands, as well as new reactions.

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Enantioselective Synthesis of Planar-Chiral Phosphines with 1,N-Dioxa[N]paracyclophane Scaffold and Their Application as Chiral Ligands

Cited by 13 publications

References 53 publications

Enantioselective Synthesis of Planar Chiral Macrocyclic Metacyclophanes by Pd-Catalyzed C–O Cross-Coupling

Enantioselective Synthesis of Planar Chiral Macrocyclic Metacyclophanes by Pd-Catalyzed C–O Cross-Coupling

Asymmetric Synthesis of Planar Chiral and Helically Chiral Compounds

Atroposelective Synthesis of Planar‐Chiral Indoles via Carbene Catalyzed Macrocyclization

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