Helical Bisphosphinites in Asymmetric Tsuji‐Trost Allylation: a Remarkable P:Pd Ratio Effect

Medena, Caleb; Aubert, Corinne; Derat, Étienne; Fensterbank, Louis; Gontard, Geoffrey; Khaled, Omar; Ollivier, Cyril; Vanthuyne, Nicolas; Petit, Marc; Barbazanges, Marion

doi:10.1002/cctc.202101072

Cited by 6 publications

(1 citation statement)

References 45 publications

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“…Helicenes are chiral; as a result, they are expected to have specific functionalities. Recently, helicenes have been widely applied in various fields [ 1 , 2 , 3 , 4 , 5 ], such as organic semiconductors [ 6 , 7 , 8 , 9 , 10 ], asymmetric catalysis [ 11 , 12 , 13 , 14 , 15 , 16 ], and molecular recognition [ 17 , 18 , 19 , 20 , 21 , 22 ], due to their diverse functionalities in materials. Many studies have also been reported on self-assembly phenomena at metal surfaces [ 23 , 24 , 25 , 26 ] caused by interactions with the π-orbitals of helicenes.…”

Section: Introductionmentioning

confidence: 99%

Intrinsic Dynamic and Static Nature of π···π Interactions in Fused Benzene-Type Helicenes and Dimers, Elucidated with QTAIM Dual Functional Analysis

Nishide

Hayashi

2022

Nanomaterials

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The intrinsic dynamic and static nature of the π···π interactions between the phenyl groups in proximity of helicenes 3–12 are elucidated with the quantum theory of atoms-in-molecules dual functional analysis (QTAIM-DFA). The π···π interactions appear in C-*-C, H-*-H, and C-*-H, with the asterisks indicating the existence of bond critical points (BCPs) on the interactions. The interactions of 3–12 are all predicted to have a p-CS/vdW nature (vdW nature of the pure closed-shell interaction), except for 2Cbay-*-7Cbay of 10, which has a p-CS/t-HBnc nature (typical-HBs with no covalency). (See the text for definition of the numbers of C and the bay and cape areas.) The natures of the interactions are similarly elucidated between the components of helicene dimers 6:6 and 7:7 with QTAIM-DFA, which have a p-CS/vdW nature. The characteristic electronic structures of helicenes are clarified through the natures predicted with QTAIM-DFA. Some bond paths (BPs) in helicenes appeared or disappeared, depending on the calculation methods. The static nature of Ccape-*-Ccape is very similar to that of Cbay-*-Cbay in 9–12, whereas the dynamic nature of Ccape-*-Ccape appears to be very different from that of Cbay-*-Cbay. The results will be a guide to design the helicene-containing materials of high functionality.

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Section: Introductionmentioning

confidence: 99%

Intrinsic Dynamic and Static Nature of π···π Interactions in Fused Benzene-Type Helicenes and Dimers, Elucidated with QTAIM Dual Functional Analysis

Nishide

Hayashi

2022

Nanomaterials

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Enantioselective Au‐Catalyzed Synthesis of Thia[5]‐ and Thia[6]helicenes and Their Transformation into Bowl‐shaped Pleiadenes

Pelliccioli

Geyso

et al. 2023

Advanced Materials

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A series of helically shaped benzo[b]chryseno[4,3‐d]thiophenes, naphtho[1,2‐b]phenanthro[4,3‐d]thiophenes, and chryseno[3,4‐b]naphtho[1,2‐d]thiophenes is synthesized via a highly enantioselective Au‐catalyzed intramolecular alkyne hydroarylation reaction. The inversion barriers of the structures obtained are determined both theoretically and experimentally, and their chiroptical properties are reported. Preliminary studies on the post‐synthetic functionalization of these thiahelicenes and their transformation into azahelicenes are also presented. In addition, a straightforward one‐step protocol is developed, which wraps the initially obtained chryseno[3,4‐b]naphtho[1,2‐d]thiophenes into bowl‐shaped pleiadene derivatives without erosion of the enantiopurity. The number of structurally related products that are obtained with high enantioselectivity enables the establishment of comprehensive correlations between the structure and conformational stability or (chir)optical properties.

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Oxidation of an Internal‐Edge‐Substituted [5]Helicene‐Derived Phosphine Synchronously Enhances Circularly Polarized Luminescence

Usui

Narita

Eto

et al. 2022

Chemistry A European J

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Small chiral organic molecules with CD properties are in high demanded due to their potential use in promising electronic and biological applications. Herein, we reveal a system in which the oxidation of a phosphino group to the corresponding phosphine oxide on the inner rim of a helicene derivative induces a CPL response. Laterally π-extended 7,8dihydro[5]helicenes bearing phosphine and phosphine oxide groups on their inner helical rims (i. e., the C1 position) were synthesized, and their helical structures were unambiguously determined by X-ray crystallography. The photophysical (UV/ visible and emission) and chiroptical properties of these compounds were investigated in various solvents. Despite their structural similarities, phosphine oxide showed a significantly better CPL response than phosphine, with a high dissymmetry factor for emission (j g lum j = (1.3-1.9) × 10 À 3 ) that can be attributed to structural changes in the interior of the helicene helix.

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Helical Bisphosphinites in Asymmetric Tsuji‐Trost Allylation: a Remarkable P:Pd Ratio Effect

Cited by 6 publications

References 45 publications

Intrinsic Dynamic and Static Nature of π···π Interactions in Fused Benzene-Type Helicenes and Dimers, Elucidated with QTAIM Dual Functional Analysis

Intrinsic Dynamic and Static Nature of π···π Interactions in Fused Benzene-Type Helicenes and Dimers, Elucidated with QTAIM Dual Functional Analysis

Enantioselective Au‐Catalyzed Synthesis of Thia[5]‐ and Thia[6]helicenes and Their Transformation into Bowl‐shaped Pleiadenes

Oxidation of an Internal‐Edge‐Substituted [5]Helicene‐Derived Phosphine Synchronously Enhances Circularly Polarized Luminescence

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