Ligand-Controlled Enantioselective Copper-Catalyzed Hydroboration and Ring-Opening Dihydroboration of Arylidenecyclobutanes DOI
Wenrui Zheng, Yuhan Cao,

Boon Beng Tan

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 25, 2025

Arylidenecyclobutanes are readily accessible and versatile reagents in synthetic chemistry due to the multifaceted reactivity exhibited by their alkene strained cyclobutane moieties. However, metal-catalyzed enantioselective functionalization of arylidenecyclobutanes, particularly controllable ring-retaining ring-opening reactions, is rarely explored. Considering utility enantioenriched organoboronate compounds, herein we report ligand-controlled copper-catalyzed hydroboration dihydroboration reactions arylidenecyclobutanes that afford chiral α-cyclobutyl benzylboronate 1,5-diboronate compounds with high enantioselectivity when (S)-DTBM-Segphos (S,S)-Ph-BPE employed, respectively. Mechanistic studies reveal process via β-C elimination significantly slower than arylidenecyclopropanes presence CuOAc (S,S)-Ph-BPE. The these two protocols further demonstrated through conducting various stereospecific site-selective transformations organoboron products, including concise synthesis bioactive molecules.

Язык: Английский

Transition-metal-catalyzed atroposelective synthesis of axially chiral styrenes DOI
Pu‐Fan Qian, Tao Zhou, Bing‐Feng Shi

и другие.

Chemical Communications, Год журнала: 2023, Номер 59(85), С. 12669 - 12684

Опубликована: Янв. 1, 2023

Recent advances in the asymmetric synthesis of axially chiral styrenes catalyzed by transition metals were summarized.

Язык: Английский

Процитировано

42
Ni-catalysed assembly of axially chiral alkenes from alkynyl tetracoordinate borons via 1,3-metallate shift DOI

Xingxing Ma,

Mengwei Tan,

Luo Li

и другие.

Nature Chemistry, Год журнала: 2024, Номер 16(1), С. 42 - 53

Опубликована: Янв. 1, 2024

Язык: Английский

Процитировано

27
Photocatalytic Z/E isomerization unlocking the stereodivergent construction of axially chiral alkene frameworks DOI Creative Commons
Jie Wang,

Jun Gu,

Jiayu Zou

и другие.

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Апрель 16, 2024

Abstract The past century has witnessed a large number of reports on the Z / E isomerization alkenes. However, vast majority them are still limited to di- and tri-substituted stereospecific tetrasubstituted alkenes remains be an underdeveloped area, thus lacking in stereodivergent synthesis axially chiral Herein we report atroposelective alkene analogues by asymmetric allylic substitution-isomerization, followed their via triplet energy transfer photocatalysis. In this regard, N -vinylquinolinones is achieved efficiently. Mechanistic studies indicate that benzylic radical generation distribution two key factors for preserving enantioselectivities compounds.

Язык: Английский

Процитировано

18
Control of Axial Chirality through NiH-Catalyzed Atroposelective Hydrofunctionalization of Alkynes DOI

Feng‐Tao Sheng,

Shi‐Chao Wang,

Junqian Zhou

и другие.

ACS Catalysis, Год журнала: 2023, Номер 13(6), С. 3841 - 3846

Опубликована: Март 3, 2023

Catalytic asymmetric hydrofunctionalization of alkenes is a well-established method with which to construct complex C(sp3)-enriched molecules central chirality. In contrast, the use catalytic abundant alkyne substrates produce valuable multisubstituted axial chirality remains largely unexplored. Here, we report general procedure this type catalyzed by Ni(II) salts and employing structurally simple chiral PyrOx ligand. A wide variety diverse atropisomeric styrenes have been obtained from hydroarylation alkynes high efficiency, complete Z-selectivity, excellent enantioselectivity.

Язык: Английский

Процитировано

34
Synthetic strategies and mechanistic studies of axially chiral styrenes DOI Creative Commons

Zi-Hao Li,

Quan‐Zhe Li,

He‐Yuan Bai

и другие.

Chem Catalysis, Год журнала: 2023, Номер 3(6), С. 100594 - 100594

Опубликована: Апрель 6, 2023

Язык: Английский

Процитировано

27
Unlocking Diverse π-Bond Enrichment Frameworks by the Synthesis and Conversion of Boronated Phenyldiethynylethylenes DOI

Jinhui Xie,

Wangyang Li, Yong Lu

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(14), С. 10167 - 10176

Опубликована: Март 27, 2024

The π-bond enrichment frameworks not only serve as a crucial building block in organic synthesis but also assume pivotal role the fields of materials science, biomedicine, photochemistry, and other related disciplines owing to their distinctive structural characteristics. incorporation various substituents into C═C double bonds tetrasubstituted alkenes is currently highly significant research area. However, with diverse on poses challenge achieving stereoselectivity. Here, we reported an efficient convergent route Cu-catalyzed borylalkynylation both symmetrical unsymmetrical 1,3-diynes, B2pin2, acetylene bromide construction boronated phenyldiethynylethylene (BPDEE) derivatives excellent chemo-, stereo-, regioselectivities. BPDEE could transform novel π-conjugated gem-diphenyldiethynylethylene (DPDEE), vinylphenyldiethynylethylene (VPDEE), phenyltriethynylethylene (PTEE) by stepwise process, which provides flexible platform for complex that were difficult synthesize previous methods. initial optical characterization revealed synthesized molecules exhibited aggregation-induced emission (AIE) properties, further establishes groundwork future applications enriches advances field functional research.

Язык: Английский

Процитировано

14
Chemo-, regio- and stereoselective access to polysubstituted 1,3-dienes via Nickel-catalyzed four-component reactions DOI Creative Commons
Shanglin Chen, Yanan Wang,

Jinhui Xie

и другие.

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июнь 28, 2024

1,2-Difunctionalization of alkynes offers a straightforward approach to access polysubstituted alkenes. However, simultaneous multi-component cascade transformations including difunctionalization two with both syn- and anti-selectivity in one catalyst system is undeveloped proves be significant challenge. Herein, we report Nickel-catalyzed four-component reaction 1,3-dienes using terminal alkynes, aryl boroxines, perfluoroalkyl iodides, wherein the forms three new C-C bonds single vessel serve as modular strategy excellent chemoselectivity, good regioselectivity exclusive stereoselectivity. Control experiments reveal plausible mechanism DFT calculations explain cause for formation this unusual reaction. Furthermore, successfully incorporate biologically active units into 1,2,3,4-tetrasubstituted 1,3-dienes, which greatly increases diversity molecular scaffolds brings more potential values medicinal chemistry, synthetic utility our protocol further demonstrated by late-stage transformations.

Язык: Английский

Процитировано

9
Synthesis of Alkene Atropisomers with Multiple Stereogenic Elements via Catalytic Asymmetric Rearrangement of 3‐Indolylmethanols DOI
Ping Wu,

Wen‐Tao Zhang,

Jixiang Yang

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Июль 23, 2024

Abstract Catalytic enantioselective preparation of alkene atropisomers with multiple stereogenic elements and discovery their applications have become significant but challenging issues in the scientific community due to unique structures this class atropisomers. We herein report first catalytic atroposelective cyclopentenyl[ b ]indoles, a new kind atropisomers, point axial chirality via an unusual rearrangement reaction 3‐indolylmethanols under asymmetric organocatalysis. Notably, novel type promising developing chiral ligands or organocatalysts, discovering antitumor drug candidates fluorescence imaging materials. Moreover, theoretical calculations elucidated possible mechanism non‐covalent interactions control enantioselectivity. This approach offers synthetic strategy for elements, represents 3‐indolylmethanols, which will advance chemistry indole chemistry.

Язык: Английский

Процитировано

9
Asymmetric Sulfonylation from a Reaction of Cyclopropan-1-ol, Sulfur Dioxide, and 1-(Alkynyl)naphthalen-2-ol DOI
Chun Zhang, Shengqing Ye, Jie Wu

и другие.

Organic Letters, Год журнала: 2024, Номер 26(15), С. 3321 - 3325

Опубликована: Апрель 10, 2024

Asymmetric sulfonylation from a reaction of cyclopropan-1-ol, sulfur dioxide, and 1-(alkynyl)naphthalen-2-ol in the presence catalytic amount organocatalyst at room temperature is developed. Axially chiral (S)-(E)-1-(1-(alkylsulfonyl)-2-arylvinyl)naphthalen-2-ols are generated moderate to good yields with excellent enantioselectivity regioselectivity under mild conditions. During this transformation, γ-keto sulfinate situ cyclopropan-1-ol dioxide acts as key intermediate.

Язык: Английский

Процитировано

8
Copper- and Palladium-Cocatalyzed Chemo-, Regio-, Stereo-, and Atroposelective Arylboration of 1,3-Enynes DOI
Wangyang Li, Haohua Chen,

Yanping Zheng

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(15), С. 11318 - 11331

Опубликована: Июль 15, 2024

Catalytic enantioselective borylation reactions of unsaturated bonds as powerful tools for the synthesis diverse chiral organoboron compounds have gained much attention and wide applications in various fields. However, atroposelective arylboration reaction with carbon–carbon triple 1,3-enynes to obtain axially 1,3-dienylboronates remains an elusive significant challenge. Hence, we develop a cooperative copper- palladium-catalyzed assemble plentiful function enriched single step from easily available 1,3-enynes, B2pin2, aryl bromides high levels chemo-, regio-, stereo-, atroposelectivity. The mild conditions lead good functional group tolerance, which is proven by broad substrate scope late-stage functionalizations bioactive or drug molecules. Moreover, can be scaled up, series further transformations achieved. It worth emphasizing that several olefin catalysts ligands axial chirality also synthesized through corresponding elaborations such products, explains transformative ability application potential 1,3-dienylboronates. mechanism experiment density theory (DFT) calculations revealed process copper palladium catalysis, indicating chemoselectivity regioselectivity boration are determined enyne insertion on copper, atroposelectivity controlled reductive elimination center. Meanwhile, calculation demonstrated distinct interactions between P═O C═O groups Pd Bpin center key transition state formation products varying configurations while employing identical configuration ligands.

Язык: Английский

Процитировано

8