Enantiopure Turbo Chirality Targets in Tri-Propeller Blades: Design, Asymmetric Synthesis, and Computational Analysis DOI Creative Commons
Yu Wang, Xu Ting, Ankit Pandey

et al.

Molecules, Journal Year: 2025, Volume and Issue: 30(3), P. 603 - 603

Published: Jan. 29, 2025

Enantiopure turbo chirality in small organic molecules, without other chiral elements, is a fascinating topic that has garnered significant interest within the chemical and materials science community. However, further research into application of this concept have been severely limited by lack effective asymmetric tools. To date, only few enantiomers targets isolated, these were obtained through physical separation using HPLC, typically on milligram scales. In work, we report first approach to enantiopure absence elements such as central axial chirality. This demonstrated assembling aromatic phosphine oxides, where three propeller-like groups are anchored P(O) center via axes. Asymmetric induction was successfully carried out sulfonimine auxiliary, with absolute configurations conformations unambiguously determined X-ray diffraction analysis. The resulting frameworks exhibit propellers arranged either clockwise (P,P,P) or counterclockwise (M,M,M) configuration. arrangements, bulkier sides rings oriented toward oxygen atom P=O bond rather than opposite direction. Additionally, orientational configuration controlled auxiliary well, showing one Naph pushed away from group (-CH2-NHSO2-tBu) phenyl ring. Computational studies conducted relative energies for rotational barriers target along axis transition pathway between two enantiomers, meeting our expectations. work expected impact fields chemistry, biomedicine, future.

Language: Английский

Enantioselective Synthesis of Secondary β-Trifluoromethyl Alcohols via Catalytic Asymmetric Reductive Trifluoroalkylation and Diastereoselective Reduction DOI
Bingbing Wu, Jie Xu,

Kang‐Jie Bian

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(14), P. 6543 - 6550

Published: April 4, 2022

Fluorinated motifs are frequently encountered in drugs and agrochemicals. Incorporating fluorine-containing drug candidates for lead optimization pharmaceutical research development has emerged as a powerful tool. The construction of molecules that feature trifluoromethyl (CF3-) group on stereogenic carbon accumulated broad efforts. Unlike its well-explored, biologically active methyl counterpart, asymmetric β-trifluoromethylated alcohols bearing adjacent stereocenters still remains elusive. Through retrosynthetic analysis, we posited followed by sequential reduction carbonyl, the initial chiral α-trifluoromethylated ketones could render desired product facile, one-pot fashion. Herein, developed first example nickel-catalyzed asymmtric reductive cross-coupling trifluoroalkylation acyl chlorides enantioselective synthesis diverse ketones. these furnished corresponding β-CF3-substituted carbons with excellent diastereoselectivity complete retention. High yields/enantioselectivity, mild conditions, good functional compatibility shown system. Utilities method also illustrated applying asymmetric, late-stage complex molecules, revealing tremendous potential CF3-containing drugs.

Language: Английский

Citations

50
Recent advances in iridium-catalyzed enantioselective allylic substitution using phosphoramidite-alkene ligands DOI
Takahiro Sawano, Ryo Takeuchi

Catalysis Science & Technology, Journal Year: 2022, Volume and Issue: 12(13), P. 4100 - 4112

Published: Jan. 1, 2022

This minireview describes the recent progress of iridium-catalyzed enantioselective allylic substitution using phosphoramidite-alkene ligands realizing highly carbon–carbon and carbon–heteroatom bond formation.

Language: Английский

Citations

47
Copper-Catalyzed Yne-Allylic Substitutions Using Stabilized Nucleophiles DOI

Shengtong Niu,

Yingkun Luo,

Chao Xu

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(12), P. 6840 - 6850

Published: May 25, 2022

Using stabilized "soft" nucleophiles in copper-catalyzed allylic substitutions is highly desirable but remains an unsolved challenge for the last 40 years. In this work, a general protocol of using such as indoles, pyrroles, amines, and 1,3-dicarbonyls has been developed, delivering large variety functionalized 1,3- 1,4-enynes with high levels regio- stereoselectivities (67 examples). A range further transformations products can be easily achieved to release various molecules. mechanistic rationale copper acetylide-bonded cation key intermediate that features outer-sphere nucleophilic attack proposed. Additionally, series diversified reactivities have demonstrated, which will inspire studies.

Language: Английский

Citations

40
Stereodivergent Construction of 1,3‐Chiral Centers via Tandem Asymmetric Conjugate Addition and Allylic Substitution Reaction DOI
Jia‐Hao Xie,

Yi‐Ming Hou,

Zuolijun Feng

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(10)

Published: Jan. 4, 2023

Herein, we report a synthesis of cyclohexanones bearing multi-continuous stereocenters by combining copper-catalyzed asymmetric conjugate addition dialkylzinc reagents to cyclic enones with iridium-catalyzed allylic substitution reaction. Good excellent yields, diastereoselectivity and enantioselectivity can be obtained. Unlike the stereodivergent construction adjacent (1,2-position) reported in literature, current reaction achieve nonadjacent (1,3-position) proper combination two chiral catalysts different enantiomers.

Language: Английский

Citations

34
Enantioselective remote methylene C−H (hetero)arylation of cycloalkane carboxylic acids DOI
Tao Zhang,

Zi‐Yu Zhang,

Guowei Kang

et al.

Science, Journal Year: 2024, Volume and Issue: 384(6697), P. 793 - 798

Published: May 16, 2024

Stereoselective construction of γ- and δ-stereocenters in carbonyl compounds is a pivotal objective asymmetric synthesis. Here, we report chiral bifunctional oxazoline-pyridone ligands that enable enantioselective palladium-catalyzed remote γ-C−H (hetero)arylations free cycloalkane carboxylic acids, which are essential carbocyclic building blocks organic The reaction establishes γ-tertiary α-quaternary stereocenters simultaneously up to >99% enantiomeric excess, providing access wide range cyclic synthons bioactive molecules. sequential editing two methylene C–H bonds can be achieved by using with opposite configuration construct carbocycles containing three centers. Enantioselective δ-C−H (hetero)arylation also realized establish particularly challenging classical methodologies.

Language: Английский

Citations

15
Molecular Editing of Ketones through N-Heterocyclic Carbene and Photo Dual Catalysis DOI
Qing‐Zhu Li,

Mei-Hao He,

Rong Zeng

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(32), P. 22829 - 22839

Published: Aug. 1, 2024

The molecular editing of ketones represents an appealing strategy due to its ability maximize the structural diversity ketone compounds in a straightforward manner. However, developing efficient methods for arbitrary modification ketonic molecules, particularly those integrated within complex skeletons, remains significant challenge. Herein, we present unique recasting that involves radical acylation

Language: Английский

Citations

15
Catalytic Enantioselective Primary C–H Borylation for Acyclic All-Carbon Quaternary Stereocenters DOI

Yuhuan Yang,

Jingyao Chen,

Yongjia Shi

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(2), P. 1635 - 1643

Published: Jan. 5, 2024

Creating a perfect catalyst to operate enzyme-like chiral recognition has been long-sought aim. A challenging example in this context is constructing acyclic all-carbon quaternary stereogenic centers by transition metal-catalyzed enantioselective C–H activation. We now report highly iridium-catalyzed primary borylation of α-all-carbon substituted 2,2-dimethyl amides enabled tailor-made bidentate boryl ligand (CBL). The success the current transformation attributed CBL/iridium catalyst, which confined pocket. This protocol provides diverse array stereocenters with excellent enantiocontrol and distinct structural features. Computational study reveals that steric hindrance CBL could regulate type dominant orbital interaction between substrate, crucial conferring high induction.

Language: Английский

Citations

13
Selectivity Separation of Ortho-Chlorotoluene Using Nonporous Adaptive Crystals of Hybrid[3]arene DOI
Yuhao Wang,

Sha Wu,

Shiqi Wei

et al.

Chemistry of Materials, Journal Year: 2024, Volume and Issue: 36(3), P. 1631 - 1638

Published: Jan. 18, 2024

Ortho-chlorotoluene serves as a vital raw material in the petrochemical industries. However, due to alkylation and chlorination, ortho-chlorotoluene is often mixed with meta-chlorotoluene para-chlorotoluene. The selective separation of from chlorotoluene isomers crucial step industrial production. owing close boiling points isomers, traditional methods demand large amount energy. Therefore, there an urgent need develop new achieve efficient isomers. Herein, we developed adsorptive strategy using nonporous adaptive crystals hybrid[3]arene H (Hα). Hα was proved be highly effective binary or ternary mixture Single-crystal structure analysis electrostatic potential maps indicated that selectivity derived stable host–guest between H. Besides, exhibited high recyclability reversible transformation guest-free guest-contained structures.

Language: Английский

Citations

10
Stereodivergent Construction of 1,5/1,7‐Nonadjacent Tetrasubstituted Stereocenters Enabled by Pd/Cu‐Cocatalyzed Asymmetric Heck Cascade Reaction DOI
Panpan Li,

Zijiao Liu,

Xiaohong Huo

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(35)

Published: May 16, 2024

Abstract The construction of chiral motifs containing nonadjacent stereocenters in an enantio‐ and diastereoselective manner has long been a challenging task synthetic chemistry, especially with respect to their stereodivergent synthesis. Herein, we describe protocol that enables the 1,5/1,7‐nonadjacent tetrasubstituted through Pd/Cu‐cocatalyzed Heck cascade reaction. Notably, C=C bond relay strategy involving shift π‐allyl palladium intermediate was successfully applied asymmetric 1,7‐nonadjacent stereocenters. current method allows for efficient preparation molecules bearing two privileged scaffolds, oxindoles non‐natural α‐amino acids, good functional group tolerance. full complement four stereoisomers products could be readily accessed by simple combination metal catalysts different enantiomers.

Language: Английский

Citations

10
Observation of unusual outer-sphere mechanism using simple alkenes as nucleophiles in allylation chemistry DOI Creative Commons
Yaxin Zeng, Han Gao, Zhong‐Tao Jiang

et al.

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

Published: May 21, 2024

Abstract Transition-metal catalyzed allylic substitution reactions of alkenes are among the most efficient methods for synthesizing diene compounds, driven by inherent preference an inner-sphere mechanism. Here, we present a demonstration outer-sphere mechanism in Rh-catalyzed reaction simple using gem -difluorinated cyclopropanes as allyl surrogates. This unconventional offers opportunity fluorine recycling via C − F bond cleavage/reformation, ultimately delivering carbofluorination products. The developed method tolerates wide range alkenes, providing access to secondary, tertiary fluorides and -difluorides with 100% atom economy. DFT calculations reveal that formation goes through unusual nucleophilic allyl-Rh species instead migration insertion, generated carbon cation then forms tetrafluoroborate fluoride shuttle.

Language: Английский

Citations

9