Synthesis of Ferrocene 1,3‐Derivatives by Distal C−H Activation** DOI

Princi Gupta,

Suchithra Madhavan, Manmohan Kapur

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(34)

Published: June 27, 2023

Abstract The third position of cyclopentadienyl ring a monosubstituted ferrocene has remained as an inaccessible chemical space for direct functionalization. Until recently, functionalizing the C(3)‐position while bypassing predominantly active C(2)‐position is most challenging task. Herein, we report distal C−H functionalization ferrocenes using easily removable directing group with precise site‐selectivity, under Pd II / mono‐ N ‐protected amino‐acid ligand catalytic system. robust synthetic protocol leads to synthesis 1,3‐derivatives broad scope in olefins ferrocenyl methylamine moderate good yields via highly strained appended 12‐membered palladacycle intermediate.

Language: Английский

Rhodium-Catalyzed Asymmetric C–H Functionalization Reactions DOI
Chen‐Xu Liu,

Si‐Yong Yin,

Fangnuo Zhao

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(16), P. 10079 - 10134

Published: Aug. 1, 2023

This review summarizes the advancements in rhodium-catalyzed asymmetric C–H functionalization reactions during last two decades. Parallel to rapidly developed palladium catalysis, rhodium catalysis has attracted extensive attention because of its unique reactivity and selectivity reactions. In recent years, Rh-catalyzed have been significantly many respects, including catalyst design, reaction development, mechanistic investigation, application synthesis complex functional molecules. presents an explicit outline catalysts ligands, mechanism, scope coupling reagents, applications.

Language: Английский

Citations

117
Explicit Mechanism of Rh(I)-Catalyzed Asymmetric C–H Arylation and Facile Synthesis of Planar Chiral Ferrocenophanes DOI
Chen‐Xu Liu, Pei‐Pei Xie,

Fangnuo Zhao

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(8), P. 4765 - 4773

Published: Feb. 14, 2023

Mechanism-guided reaction development is a well-appreciated research paradigm in chemistry since the merging of mechanistic knowledge would accelerate discovery new synthetic methods. Low-valent transition metals such as Pd(0)- and Rh(I)-catalyzed C–H arylation with aryl (pseudo)halides among enabling reactions for exclusive cross-coupling two different partners. However, from situation Pd(0)-catalysis, mechanism underexplored. The sequence elementary steps activation oxidative addition remains unclear. Herein, we report comprehensive experimental computational studies toward explicit understandings intermolecular asymmetric between 2-pyridinylferrocenes bromides. identification each step catalytic cycle structural characterization key intermediates states allow rational design challenging intramolecular reactions. successful realization this mode set foundation facile synthesis planar chiral [m]ferrocenophanes (m = 6–8), class rarely explored target molecules strained structures intriguing molecular topology.

Language: Английский

Citations

28
Copper/BINOL-Catalyzed Enantioselective C–H Functionalization toward Planar Chiral Ferrocenes Under Mild Conditions DOI
Zhuo‐Zhuo Zhang, Gang Zhou, Qiang Yue

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(6), P. 4030 - 4039

Published: Feb. 28, 2024

Copper-catalyzed enantioselective C–H activation proceeding through an inner-sphere mechanism remains a huge challenge. Herein, copper-catalyzed alkynylation with terminal alkynes assisted by 8-aminoquinoline using readily available (S)-BINOL as the chiral ligand was disclosed. The reaction proceeded under mild conditions catalytic amount of copper salt, providing range ferrocenes in good yields and enantioselectivities (0 °C, up to 77% yield 94% ee). alteration stoichiometric chemical oxidant renewable electricity is also feasible at ambient temperature, demonstrating robustness this copper/BINOL catalysis. Notably, first cupraelectrocatalyzed reaction. Gram-scale synthesis, versatile transformations, application resulting oxazoline–olefin asymmetric synthesis highlight utility protocols.

Language: Английский

Citations

15
Recent advances in Rh(i)-catalyzed enantioselective C–H functionalization DOI Creative Commons
Yue Zhang, Jing‐Jing Zhang, Lujun Lou

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(7), P. 3457 - 3484

Published: Jan. 1, 2024

Chiral carbon-carbon (C-C) and carbon-heteroatom (C-X) bonds are pervasive very essential in natural products, bioactive molecules, functional materials, their catalytic construction has emerged as one of the hottest research fields synthetic organic chemistry. The last decade witnessed vigorous progress Rh(I)-catalyzed asymmetric C-H functionalization a complement to Rh(II) Rh(III) catalysis. This review aims provide most comprehensive up-to-date summary covering recent advances activation for functionalization. In addition development diverse reactions, chiral ligand design mechanistic investigation (inner-sphere mechanism, outer-sphere 1,4-Rh migration) will also be highlighted.

Language: Английский

Citations

13
Specific Discrimination Polymerization for Highly Isotactic Polyesters Synthesis DOI
Xuanhua Guo, Guangqiang Xu,

Rulin Yang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(13), P. 9084 - 9095

Published: March 1, 2024

Isotactic polymers have emerged with unique and excellent properties in material sciences. Specific discrimination polymerization provides an ideal pathway to achieve highly isotactic from their racemic monomers, which is of great significance a challenge polymeric chemistry. Although enantioselective catalyst-mediated asymmetric kinetic resolution (AKRP) process makes it possible, general well-defined strategy for catalyst design still rarely reported. Here, based on novel dual-ligand strategy, new type chiral (BisSalen)Al complex high enantioselectivity has been described, perfect AKRP phenethylglycolide (Pegl) achieved the first time. The more confined microenvironment formed by dual ligand key improve original catalyst. To illustrate generality this series complexes homo- or heterodual ligands were designed Pegl.

Language: Английский

Citations

12
Enantioselective functionalization of unactivated C(sp3)–H bonds through copper-catalyzed diyne cyclization by kinetic resolution DOI Creative Commons

Yang‐Bo Chen,

Li‐Gao Liu,

Zhe-Qi Wang

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: March 12, 2024

Site- and stereoselective C-H functionalization is highly challenging in the synthetic chemistry community. Although of vinyl cations has been vigorously studied C(sp

Language: Английский

Citations

11
P(III)-Directed Asymmetric C–H Arylation toward Planar Chiral Ferrocenes by Palladium Catalysis DOI

Xueli Lv,

Minyan Wang, Yue Zhao

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 3483 - 3491

Published: Jan. 24, 2024

Planar chiral ferrocenyl phosphines have been employed as highly valuable ligands in metal-catalyzed asymmetric reactions. However, their preparation remains a formidable challenge due to the requirement for intricate, multistep synthetic sequences. In addressing this issue, we developed groundbreaking enantioselective C-H activation strategy facilitated by P(III) directing groups, enabling efficient construction of planar single step. Our innovative approach entails combination palladium catalyst, parent phosphine, and phosphoramidite ligand, leading exceptional reactivity enantioselectivity. Remarkably, these novel exhibit remarkable efficacy silver-catalyzed 1,3-dipolar cycloadditions. We carried out experimental computational studies obtain more comprehensive understanding reaction pathway factors contributing

Language: Английский

Citations

9
Nickel‐Catalyzed Kinetic Resolution of Racemic Unactivated Alkenes via Enantio‐, Diastereo‐, and Regioselective Hydroamination DOI
Hyung‐Joon Kang, Changseok Lee, Sungwoo Hong

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(24)

Published: April 20, 2023

Abstract Kinetic resolution is a powerful strategy for the isolation of enantioenriched compounds from racemic mixtures, and development selective catalytic processes an active area research. Here, we present nickel‐catalyzed kinetic α‐substituted unconjugated carbonyl alkenes via enantio‐, diastereo‐, regioselective hydroamination. This protocol affords both chiral butenamides syn ‐β 2,3 ‐amino acid derivatives with high enantiomeric purity (up to 99 % ee) selectivity factor up >684. The key excellent efficiency distinctive architecture nickel complex, which enables successful enantioselective C−N bond construction. Mechanistic investigations reveal that unique structure ligand facilitates rapid migratory insertion step one enantiomer. provides practical versatile approach prepare wide range compounds.

Language: Английский

Citations

15
Enantioselective Rh(I)-Catalyzed C–H Arylation of Ferroceneformaldehydes DOI Creative Commons
Chen‐Xu Liu,

Fangnuo Zhao,

Qing Gu

et al.

ACS Central Science, Journal Year: 2023, Volume and Issue: 9(11), P. 2036 - 2043

Published: Sept. 28, 2023

As an important class of platform molecules, planar chiral ferrocene carbonyl compounds could be transformed into various functional groups offering facile synthesis ligands and catalysts. However, developing efficient straightforward methods for accessing enantiopure compounds, especially ferroceneformaldehydes, remains highly challenging. Herein, we report a rhodium(I)/phosphoramidite-catalyzed enantioselective C–H bond arylation ferroceneformaldehydes. Readily available aryl halides such as iodides, bromides, even chlorides are suitable coupling partners in this transformation, leading to series ferroceneformaldehydes good yields excellent enantioselectivity (up 83% yield >99% ee). The aldehyde group diverse smoothly, Ugi's amine PPFA analogues synthesized efficiently. latter was found ligand Pd-catalyzed asymmetric allylic alkylation reactions. Mechanistic experiments supported the formation imine intermediates key step during reaction.

Language: Английский

Citations

11
Catalytic asymmetric synthesis of planar-chiral dianthranilides via (Dynamic) kinetic resolution DOI Creative Commons

Chun-Yan Guan,

Shuai Zou,

Can Luo

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: May 29, 2024

Abstract Chirality constitutes an inherent attribute of nature. The catalytic asymmetric synthesis molecules with central, axial, and helical chirality is a topic intense interest becoming mature field research. However, due to the difficulty in lack prototype, less attention has been given planar arising from destruction symmetry on single ring. Herein, we report planar-chiral dianthranilides, unique class tub-shaped eight-membered cyclic dilactams. This protocol enabled by cinchona alkaloid-catalyzed (dynamic) kinetic resolution. Under mild conditions, various C 2 - or 1 -symmetric dianthranilides have readily prepared high yields excellent enantioselectivity. These can serve as addition family molecules. Its synthetic value demonstrated resolution racemic amines via acyl transfer, enantiodivergent natural product eupolyphagin, preliminary antitumor activity studies.

Language: Английский

Citations

4