Introduction DOI
Mohamed S. H. Salem, Shinobu Takizawa

Опубликована: Окт. 18, 2024

Atropisomerism, arising from hindered rotation about single bonds, is a crucial element of molecular chirality with far-reaching implications across scientific disciplines. This opening chapter elucidates the foundational concepts underpinning atropisomerism and chirality, laying groundwork for subsequent discussions. Furthermore, it outlines diverse atroposelective synthetic methodologies, encompassing metal-based organocatalytic oxidative coupling, cross-coupling, ring-opening reactions, which receive detailed consideration in chapters, thus underscoring breadth research this domain. Recent advancements field are highlighted, underlining growing recognition atropisomerism's multifaceted applications. Additionally, addresses persistent challenges impeding further control synthesis, along its expanding applications drug industry development.

Язык: Английский

Enantioselective Synthesis of Axially Chiral Alkylidenecycloalkanes via Copper-Catalyzed Functionalization of Acyl Allenols DOI

Baihui Gong,

Qing‐Bin Lu,

R. Li-jiun Sun

и другие.

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 2351 - 2358

Опубликована: Янв. 24, 2025

Язык: Английский

Процитировано

3
Enantioselective Construction of Anthracenylidene-Based Axial Chirality by Asymmetric Heck Reaction DOI

Shi-Jiang He,

Boming Shen,

Lian-Zheng Zuo

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(28), С. 19137 - 19145

Опубликована: Июль 2, 2024

Anthracenylidene is an intriguing structural unit with potential in various fields. The study presents a novel approach to introducing axial chirality into this all-carbon core skeleton through remotely controlled desymmetrization strategy. A palladium-catalyzed enantioselective Heck arylation of exocyclic double bond anthracene two distinct substituents at the C10 position harnessed realize such transformation. judicious identification P-centrally chiral ligand pivotal ensure competitive competence reactivity and stereocontrol when heteroatom handle absent from anthracenylidene skeleton. Both mono- disubstituted substrates were compatible for established catalytic system, structurally diverse anthracenylidene-based frameworks forged good-to-high enantiocontrol. subsequent derivatization obtained products yielded valuable array centrally axially molecules, thus emphasizing practicality chemistry. DFT calculations shed light on mechanism provided insights origin experimentally observed enantioselectivity reaction.

Язык: Английский

Процитировано

9
Stable Axially Chiral Cyclohexylidenes from Catalytic Asymmetric Knoevenagel Condensation DOI

Meijia Ying,

Kaixuan Wang,

Wenjun Yan

и другие.

Chemistry - A European Journal, Год журнала: 2024, Номер 30(39)

Опубликована: Май 7, 2024

Axially chiral cycloalkylidenes are interesting but less developed axially molecules. Here, a bispidine-based amine catalytic system was to promote efficiently the asymmetric Knoevenagel condensation of N-protected oxindoles and benzofuranones with 4-substituted cyclohexanones. A variety alkylidenecycloalkanes stable axial chirality were obtained in good yields fairly er (enantiomeric ratio). Based on absolute configuration determination product DFT calculations, possible mechanism stereoselective induction proposed.

Язык: Английский

Процитировано

4
Chiral Amino Acids: Evolution in Atroposelective C-H Activation DOI
Diksha Parmar, Rohit Kumar, Upendra Sharma

и другие.

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(25), С. 5032 - 5051

Опубликована: Янв. 1, 2024

This review covers the journey of chiral amino acids as ligands in atroposelective C–H bond activation/functionalization via transition metal catalysis.

Язык: Английский

Процитировано

4
Phosphoric Acid-Catalyzed Enantioselective Synthesis of Axially Chiral Cyclobutanamides DOI

Guang Cheng,

Jinfeng Zheng,

Yilin Zhu

и другие.

Organic Letters, Год журнала: 2025, Номер 27(10), С. 2509 - 2514

Опубликована: Март 5, 2025

Chiral cyclobutanamide is a privileged scaffold in drug discovery. Here, we describe, for the first time, synthesis of axially chiral cyclobutanamides via phosphoric acid-catalyzed enantioselective condensation between N-arylcarbamyl cyclobutanones and hydroxylamines. Rational substrate design, incorporating an amide moiety (CONHR) into cyclobutanone backbone formation multi-hydrogen bonding network involving N-H this portion, responsible excellent enantioselectivity achieved stereodetermining dehydration process, which supported by detailed mechanistic study.

Язык: Английский

Процитировано

0
Rh(I)-Catalyzed Modular Synthesis of Axially Chiral Alkylidene Azacycloalkanes DOI Creative Commons
Yang Chen, Jiayan Chen, Shifa Zhu

и другие.

ACS Central Science, Год журнала: 2025, Номер unknown

Опубликована: Май 11, 2025

Язык: Английский

Процитировано

0
Enantioselective Synthesis of Axially Chiral Alkylidenecyclobutanes via Palladium-Catalyzed N-Tosylhydrazone-Based Carbene Coupling DOI

Xiaoqin Ning,

Tonglin Zhao,

Yulei Zhu

и другие.

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

Опубликована: Май 11, 2025

The synthesis of axially chiral alkylidenecyclobutanes remains challenging due to the requirement both an efficient asymmetric catalytic system and preservation its inherent strained ring structure. We herein disclose enantioselective carbene cross-coupling reaction cyclobutanecarbaldehyde-derived N-tosylhydrazones with aryl bromides, enabled by palladium catalysis in combination elaborately modified sulfinamide phosphine ligand (Sadphos). This method demonstrates feasibility constructing axial chirality on a metal intermediate precisely through sequential process enantiodetermined migratory insertion followed central-to-axial-chirality-transfer β-H elimination. provides access diverse featuring heteroatom-substituted, tertiary all-carbon quaternary stereocenter excellent yields (up 95%) high enantioselectivities 95% ee). Moreover, enantiomers can be selectively obtained choosing either cis- or trans-cyclobutane substrates stereospecific manner.

Язык: Английский

Процитировано

0
Ligand-controlled regiodivergent arylation of aryl(alkyl)alkynes and asymmetric synthesis of axially chiral 9-alkylidene-9,10-dihydroanthracenes DOI Creative Commons
Chao Sun, Ting Qi, Faiz‐Ur Rahman

и другие.

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

Опубликована: Окт. 29, 2024

Transition metal-catalyzed addition of organometallics to aryl(alkyl)alkynes has been well known proceed with the regioselectivity in forming a carbon-carbon bond at alkyl-substituted carbon (β-addition). Herein, reverse regiochemistry high selectivity giving 1,1-diarylalkenes (α-addition) was realized reaction arylboronic acids by use rhodium catalyst coordinated chiral diene ligand, whereas arylation same alkynes proceeded usual (β-addition) presence rhodium/DM-BINAP catalyst. The can be switched choice ligands on catalysts. This also enabled catalytic asymmetric synthesis phoenix-like axially alkylidene dihydroanthracenes enantioselectivity through an α-addition/1,4-migration/cyclization sequence.

Язык: Английский

Процитировано

2
Introduction DOI
Mohamed S. H. Salem, Shinobu Takizawa

Опубликована: Окт. 18, 2024

Atropisomerism, arising from hindered rotation about single bonds, is a crucial element of molecular chirality with far-reaching implications across scientific disciplines. This opening chapter elucidates the foundational concepts underpinning atropisomerism and chirality, laying groundwork for subsequent discussions. Furthermore, it outlines diverse atroposelective synthetic methodologies, encompassing metal-based organocatalytic oxidative coupling, cross-coupling, ring-opening reactions, which receive detailed consideration in chapters, thus underscoring breadth research this domain. Recent advancements field are highlighted, underlining growing recognition atropisomerism's multifaceted applications. Additionally, addresses persistent challenges impeding further control synthesis, along its expanding applications drug industry development.

Язык: Английский

Процитировано

0