Asymmetric Construction of Axially Chiral 2‐Arylpyrroles by Chirality Transfer of Atropisomeric Alkenes

Wang, Yong-Bin; Wu, Quan‐Hao; Zhou, Zhipeng; Xiang, Shao‐Hua; Cui, Yuan; Yu, Peiyuan; Tan, Bin

doi:10.1002/anie.201907470

Cited by 83 publications

(31 citation statements)

References 73 publications

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“…N-Alkylation of enamide 112 also enabled preparation of atropisomeric styrenes. 32 Nucleophilic substitution of alkyl bromides with 112 in the presence of a catalytic amount of 114 afforded enantioenriched styrenes 113 with satisfactory stereoselectivity and good functional-group tolerance (Scheme 21). Substrates including allyl bromide, propargyl bromide, 4-methoxybenzyl bromide, and benzyl bromide were successfully applied in the protocol (113a-113e).…”

Section: Review Synopenmentioning

confidence: 99%

Atropisomerism in Styrene: Synthesis, Stability, and Applications

Feng

2021

SynOpen

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Atropisomeric styrenes are a class of optically active compounds, the chirality of which results from restricted rotation of the C(vinyl)–C(aryl) single bond. In comparison with biaryl atropisomers, the less rigid skeleton of styrenes usually leads them to have lower rotational barriers. Although it has been overlooked for a long time, scientists have paid attention to this class of unique molecules in recent years and have developed many methods for the preparation of optically active atropisomeric styrenes. In this article, we review the development of the concept of atropisomeric styrenes, along with their isolation, asymmetric synthesis, and synthetic applications.1 Introduction2 The Concept of Styrene Atropisomerism3 Early Research: Separation of Optically Active Styrenes4 Synthesis of Optically Active Styrenes5 Stability of the Chirality of Atropisomeric Styrenes6 Outlook

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Section: Review Synopenmentioning

confidence: 99%

Atropisomerism in Styrene: Synthesis, Stability, and Applications

Feng

2021

SynOpen

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“…A chirality transfer strategy, somewhat related to chirality conversion strategies, was developed by Tan, Xiang, and co-workers for the preparation of axially chiral 2-arylpyrroles 65 starting from chiral enamines 64 (Scheme 15). 42 These were prepared following a DKR of configurationally unstable starting materials 62 in a phase-transfer alkylation process with bromides 63 using chiral catalyst Q. Enamines 64, bearing an alkene-arene stereogenic axis, were obtained with high efficiency and selectivity. Then, selected enamines 64 (particularly the ones bearing a propargyl moiety) were found to be useful substrates for a base-promoted cyclization towards the formation of desired products 65, now displaying an arene-arene stereogenic axis.…”

Section: Short Review Syn Thesismentioning

confidence: 99%

Organocatalytic Asymmetric Methodologies towards the Synthesis of Atropisomeric N-Heterocycles

Corti¹,

Bertuzzi

2020

Synthesis

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A perspective on the literature dealing with the organocatalytic asymmetric preparation of axially chiral N-heterocycles is provided. A particular focus is devoted to rationalize the synthetic strategies employed in each case. Moreover, specific classes of organocatalysts are shown to stand out as privileged motives for the stereoselective preparation of such synthetically challenging molecular architectures. Finally, an overview of the main trends in the field is given.1 Introduction2 Five-Membered Rings2.1 Arylation2.2 Dynamic Kinetic Resolution2.3 Ring Construction2.4 Central-to-Axial Chirality Conversion and Chirality Transfer2.5 Desymmetrization3 Six-Membered Rings3.1 Desymmetrization3.2 (Dynamic) Kinetic Resolution3.3 Ring Construction3.4 Central-to-Axial Chirality Conversion4 Conclusion

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“…Alreadyo utside of porphyrin chemistry, [13] stable atropisomers of N-aryl pyrroles were reported, [14] in which the pyrrolew as substituted at the 2-position or at the Na tom with an orthoaryl group. [15] Similarly,3 -aryl pyrrole with an additional substituenta tt he 4-position yielded separable atropisomers. [16] Thus, we presumedt hat incorporatingN -protected pyrroles in ap orphyrin at meso-position (i.e.…”

Section: Introductionmentioning

confidence: 99%

Atropisomers of meso Tetra(N‐Mesyl Pyrrol‐2‐yl) Porphyrins: Synthesis, Isolation and Characterization of All‐Pyrrolic Porphyrins

Zhu

Himmel

Merkes

et al. 2020

Chemistry A European J

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Atropisomerism has been observed in a variety of biaryl compounds and meso‐aryl substituted porphyrins. However, in porphyrins, this phenomenon had been shown only with o‐substituted 6‐membered aromatic groups at the meso‐position. We show herein that a 5‐membered heteroaromatic (N‐mesyl‐pyrrol‐2‐yl) group at the meso‐position leads to atropisomerism. In addition, we report a ‘one‐pot’ synthetic route for the synthesis of ‘all‐pyrrolic’ porphyrin (APP) with several N‐protection groups (Boc, Cbz, Ms and Ts). Among these groups, we found that only the Ms group gave four individually separable atropisomers of meso‐tetra(N‐Ms‐pyrrol‐2‐yl) porphyrin. Furthermore, the reductive removal of Cbz‐ was achieved to obtain meso‐tetra(pyrrol‐2‐yl) porphyrin. Thus, our synthetic procedure provides an easy access to a group of APPs and stable atropisomers, which is expected to expand the application of novel APP‐based materials.

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Asymmetric Construction of Axially Chiral 2‐Arylpyrroles by Chirality Transfer of Atropisomeric Alkenes

Abstract: Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Cited by 83 publications

References 73 publications

Atropisomerism in Styrene: Synthesis, Stability, and Applications

Atropisomerism in Styrene: Synthesis, Stability, and Applications

Organocatalytic Asymmetric Methodologies towards the Synthesis of Atropisomeric N-Heterocycles

Atropisomers of meso Tetra(N‐Mesyl Pyrrol‐2‐yl) Porphyrins: Synthesis, Isolation and Characterization of All‐Pyrrolic Porphyrins

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