Ni-catalysed assembly of axially chiral alkenes from alkynyl tetracoordinate borons via 1,3-metallate shift

Ma, Xingxing; Tan, Mengwei; Li, Luo; Zhong, Zihao; Li, Puhui; Liang, Jinchao; Song, Qiuling

doi:10.1038/s41557-023-01396-7

Cited by 22 publications

(1 citation statement)

References 69 publications

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“…To the best of our knowledge, an asymmetric method for catalytic enantioselective synthesis of axially chiral 1,3-dienylboronates has not yet been explored. In addition, compared with other prevalent optically atropisomeric styrenes, , the regio-, stereo-, and atroposelective synthesis of axially chiral 1,3-dienes remains elusive . To date, only very few elegant asymmetric catalytic methodologies have been disclosed to construct axially chiral 1,3-dienes; thus, the discovery of original enantioselective patterns would offer new opportunities to enrich this field, yet it remains significantly challenging.…”

Section: Introductionmentioning

confidence: 99%

Copper- and Palladium-Cocatalyzed Chemo-, Regio-, Stereo-, and Atroposelective Arylboration of 1,3-Enynes

Li,

Chen,

Zheng

et al. 2024

ACS Catal.

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Catalytic enantioselective borylation reactions of unsaturated bonds as powerful tools for the synthesis of diverse chiral organoboron compounds have gained much attention and have wide applications in various fields. However, the atroposelective arylboration reaction with carbon−carbon triple bonds of 1,3-enynes to obtain axially chiral 1,3-dienylboronates remains an elusive and significant challenge. Hence, we develop a cooperative copper-and palladium-catalyzed arylboration reaction to assemble plentiful function enriched axially chiral 1,3-dienylboronates in a single step from easily available 1,3-enynes, B 2 pin 2 , and aryl bromides with high levels of chemo-, regio-, stereo-, and atroposelectivity. The mild reaction conditions lead to good functional group tolerance, which is proven by the broad substrate scope and late-stage functionalizations of bioactive compounds or drug molecules. Moreover, the reaction can be easily scaled up, and a series of further transformations can be achieved. It is worth emphasizing that several olefin catalysts and ligands with axial chirality can also be synthesized through the corresponding elaborations of such products, which further explains the powerful transformative ability and application potential of such axially chiral 1,3-dienylboronates. The mechanism experiment and density functional theory (DFT) calculations revealed the cooperative process of copper and palladium catalysis, indicating that the chemoselectivity and regioselectivity of boration are determined by the enyne insertion step on copper, and the atroposelectivity is controlled by the further reductive elimination on the palladium center. Meanwhile, the calculation also demonstrated that the distinct interactions between the P�O and C�O groups with the Pd or Bpin center in the key transition state lead to the formation of products with varying configurations while employing identical configuration ligands.

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Section: Introductionmentioning

confidence: 99%

Copper- and Palladium-Cocatalyzed Chemo-, Regio-, Stereo-, and Atroposelective Arylboration of 1,3-Enynes

Li,

Chen,

Zheng

et al. 2024

ACS Catal.

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Catalytic and Base‐free Suzuki‐type α‐Arylation of Cyclic 1,3‐Dicarbonyls via a Cyclic Iodonium Ylide Strategy

Liang,

He,

Zhong

et al. 2024

Angewandte Chemie

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To date, it remains challenging to achieve a general and catalytic α‐arylation of cyclic 1,3‐dicarbonyls, particularly ubiquitous heteroaromatic ones. In most cases, the preparation of their medically significant arylated derivatives requires multistep synthetic sequences. Herein, we introduce a new, convenient strategy involving the conversion of cyclic 1,3‐dicarbonyls to cyclic iodonium ylides (CIYs), followed by rhodium‐catalyzed α‐arylation with arylboronic reagents via carbene coupling. This approach is mild, operationally simple, base‐free, biocompatible, and exhibits broad substrate scope (> 100 examples), especially with respect to various heteroaromatic 1,3‐dicarbonyls and ortho‐substituted or base‐sensitive arylboronic acids. Importantly, owing to the excellent compatibility with various arylboronic acids or boronate esters (ArBpin, ArBneop, or ArBF3K), this method allows the late‐stage installation of heterocyclic 1,3‐dicarbonyl motifs in highly complex settings. The utility of this transformation is further demonstrated through significantly simplifying the synthesis of several bioactive molecules and natural products.

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Organocatalytic Atroposelective Synthesis of Axially Chiral Indolyl Ketosulfoxonium Ylides

Zhang,

Huang

2024

Angewandte Chemie

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Despite recent advancements in catalytic synthesis of axial chirality, reports on non‐biaryl atropisomers remain limited because of the stringent steric requirements necessary to establish effective rotational brakes. In this study, we present a novel class of monoaryl atropisomers, indolyl ketosulfoxonium ylides, and describe an organocatalytic protocol for their synthesis. We discovered that a chiral phosphoric acid (CPA) serves as an effective catalyst for the highly enantioselective iodination of ortho‐aminophenylethynyl sulfoxonium ylides. Under the optimized reaction conditions, a strong preference for the intended iodination process over the competing protonation was observed. Subsequently, intramolecular amide cyclization enabled the formation of sterically congested indole fragments. Furthermore, the synthetic utility of the products was demonstrated by showcasing versatile transformations into other chiral scaffolds with complete retention of optical purity.

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Ni-catalysed assembly of axially chiral alkenes from alkynyl tetracoordinate borons via 1,3-metallate shift

Cited by 22 publications

References 69 publications

Copper- and Palladium-Cocatalyzed Chemo-, Regio-, Stereo-, and Atroposelective Arylboration of 1,3-Enynes

Copper- and Palladium-Cocatalyzed Chemo-, Regio-, Stereo-, and Atroposelective Arylboration of 1,3-Enynes

Catalytic and Base‐free Suzuki‐type α‐Arylation of Cyclic 1,3‐Dicarbonyls via a Cyclic Iodonium Ylide Strategy

Organocatalytic Atroposelective Synthesis of Axially Chiral Indolyl Ketosulfoxonium Ylides

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