New conformationally flexible and recyclable aryl iodine catalysts from inexpensive chiral source for asymmetric oxidations DOI Creative Commons

Hai-Jie Zhou,

Yi-Ping Yao,

Xu Wang

et al.

Research Square (Research Square), Journal Year: 2023, Volume and Issue: unknown

Published: April 24, 2023

Abstract Despite the remarkable advances in research field of asymmetric catalytic oxidation reactions via hypervalent iodines with simple procedures, high level efficiency and stereoselectivity over past few decades, development their highly scalable, environmentally benign, sustainable protocols under greener organocatalysis paradigm for further industrial translations remains a long-standing synthetic organic chemistry process engineering challenge. Herein, we design synthesize new library conformationally flexible recyclable aryl iodine catalysts by utilization (i) waste (chloramphenicol base) as scaffold (ii) inexpensive amino acid residue (threonine) chiral source. Our iodine(III) bearing H-bond donors tunable pocket have been successfully applied diverse robust oxidative transformations, e.g., dearomatization, spirolactonization, direct C(sp 2 )−H/C(sp 3 )−H cross-coupling, fluoridation. processes feature column-isolation-free approach, easy-handling operation, upscaling synthesis, being facilely recycled particular precipitation.

Language: Английский

Asymmetric Dearomatization of Nonfunctionalized 1-Naphthols via Copper-Catalyzed Enantioselective [4 + 1] Spiroannulation DOI
Xingguang Li,

Jiaxing Guo,

Jin Zhang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(12), P. 9244 - 9253

Published: June 3, 2024

Catalytic asymmetric dearomatization (CADA) is a powerful tool for the rapid construction of complex chiral three-dimensional cyclic molecules featuring quaternary carbon centers from readily available arenes. However, ubiquitous nonfunctionalized 1-naphthols to afford remains challenging and undeveloped. This study reports dearomative [4 + 1] spiroannulation via copper catalysis. reaction features highly chemo-, regio-, stereoselective nucleophilic addition intramolecular annulation cascade reactive π-extended copper-allenylidene, thus enabling practical synthesis range valuable spirocyclic enones bearing stereocenter with high efficiency. Furthermore, this protocol applicable phenols. Control experiments supported substitution-annulation mechanism by excluding process involving 1,3-sigmatropic shift. Preliminary biological activity studies indicated that synthesized hold significant promise as anticancer agents inducing tumor cell apoptosis.

Language: Английский

Citations

10
Enantioselective Copper-Catalyzed Dearomative Spiroannulation of β-Naphthols or Indoles with Yne-Allylic Esters DOI
Ruinan Zhao, Shuang Deng,

Rongkang Huang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(12), P. 9254 - 9264

Published: June 3, 2024

Catalytic asymmetric dearomatization reactions of α-unsubstituted β-naphthols are very challenging due to the high energy barrier resulting from loss aromaticity. Herein, we describe an example enantioselective catalytic dearomative spiroannulation with yne-allylic esters. The success this reaction relied on copper-catalyzed remote strategy using esters as bis-electrophilic reagents. This transformation features mild conditions, broad functional group tolerance, and extensive substrate scope, thereby facilitating efficient construction array enantioenriched naphthalene-2-one spiroindolenine derivatives. Experimental studies density theory calculations establish pathway origin stereoselectivity.

Language: Английский

Citations

9
Application of chiral recyclable catalysts in asymmetric catalysis DOI Creative Commons

GuiPing Han,

WenQi Ren,

Shengyong Zhang

et al.

RSC Advances, Journal Year: 2024, Volume and Issue: 14(23), P. 16520 - 16545

Published: Jan. 1, 2024

Chiral drugs hold a significant position within the contemporary pharmaceutical market, and chiral catalysts play crucial role in their synthesis.

Language: Английский

Citations

4
Synthesis of Diastereomeric Hydrobenzofurans and Hydronaphthofurans via an Iodine Reagent-Promoted Intramolecular Dearomatization Reaction DOI
Xinkun An, Haoyun Ma, Tingting Zhang

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 12, 2025

The first metal- and base-free construction of diastereomeric hydrobenzofurans hydronaphthofurans, which were capable further transformations to achieve natural product frameworks, was achieved by the intramolecular oxidized dearomatization phenol or naphthol derivatives via promotion iodine reagents. Enantioselective products obtained through chiral substrates catalysts. This step-economical protocol built multiple centers with extensive tolerance various substrates, resulted in a potential molecular library for developing functional polycyclic scaffolds.

Language: Английский

Citations

0
Second-Layer Chiral Environment-Induced Steric Hindrance Enables Catalyst Conformation Lockdown in Enantioselective Hypervalent Iodine Organocatalysis DOI
Xiaotao Zhang,

Miaomiao Liu,

Hao Ge

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(12), P. 8273 - 8280

Published: June 6, 2023

A class of confined chiral hypervalent iodines have been designed and developed by incorporating two sterically demanding BINOL-derived units, which form the second-layer environment, into iodine-containing molecules to lock down conformation catalyst indirectly create a compact environment around active site. Good-to-excellent enantioselectivities achieved with these catalysts for α-oxysulfonylation ketones (up 97.5:2.5 er) oxidative cyclization 5-oxo-5-arylpentanoic acids γ-butyrolactones 98:2 er), thereby demonstrating utility this strategy design.

Language: Английский

Citations

9
Chiral cobalt(ii) complex-promoted asymmetric para-Claisen rearrangement of allyl α-naphthol ethers DOI Creative Commons

Hongkun Zeng,

Lifeng Wang, Zhishan Su

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(47), P. 13979 - 13985

Published: Jan. 1, 2023

A highly enantioselective para -Claisen rearrangement of allyl α-naphthol ethers is realized by a chiral cobalt( ii )/ N , ′-dioxide complex catalyst.

Language: Английский

Citations

6
Chiral Hypoiodite Salt Catalysts for Enantioselective Oxidative Transformations DOI
Minami Odagi, Kazuo Nagasawa

ChemCatChem, Journal Year: 2023, Volume and Issue: 15(18)

Published: July 17, 2023

Abstract Iodine and its hypervalent derivatives have emerged as versatile environmentally friendly oxidative reagents in organic synthesis, offering efficient ways to form new bonds. However, the use of iodine is challenging, they are unstable, potentially explosive, costly. Therefore, hypoiodite species derived from onium iodites using safe inexpensive oxidants considered more promising for facilitating transformations. Nevertheless, applications such catalytic systems still limited scope, especially asymmetric reactions. In this concept paper, we described recent progress chiral hypoiodite‐catalyzed enantioselective bond‐forming reactions, focusing on carbon–oxygen, carbon–nitrogen, carbon–carbon bond formation reactions ammonium guanidinium salts iodites.

Language: Английский

Citations

4
Electrophile–Arene Affinity: An Energy Scale for Evaluating the Thermodynamics of Electrophilic Dearomatization Reactions DOI
Wenwen Zhang,

Zuolijun Feng,

Shu‐Li You

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(16), P. 11487 - 11501

Published: July 30, 2024

Rational design and development of organic reactions are lofty goals in synthetic chemistry. Quantitative description the properties molecules by physical parameters plays an important role this regard. In Article, we report energy scale, namely, electrophile-arene affinity (EAA), for evaluating thermodynamics electrophilic dearomatization reactions, a class transformations that can rapidly build up molecular complexity structural diversity converting planar aromatic compounds into three-dimensional cyclic molecules. The acquisition EAA data be readily achieved theoretically calculating enthalpy changes (Δ

Language: Английский

Citations

1
Electrochemical Dichlorinative Cyclization of 1,n-Enynes by 4-Iodotoluene Catalysis DOI
Xu Wang, Longji Li,

Zhongjian Du

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 28, 2024

An electrochemical approach for the indirect oxidative generation of hypervalent iodoarene as a reaction catalyst has been reported. The proceeds first from active Cl species by electro-oxidation, followed transfer to generate ArICl

Language: Английский

Citations

1
New conformationally flexible and recyclable aryl iodine catalysts from an inexpensive chiral source for asymmetric oxidations DOI

Hai-Jie Zhou,

Yi-Ping Yao,

Tonghui Zhang

et al.

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(24), P. 10447 - 10457

Published: Jan. 1, 2023

A concise, scalable and efficient process has been well established to access a new conformationally flexible recyclable aryl iodine catalyst library, which could be extensively loaded series of highly enantioselective oxidative transformations.

Language: Английский

Citations

2