Xiao-Ming Zhao’s research while affiliated with Tongji University and other places

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Publications (37)


Highly diastereoselective and enantioselective cyclopropanation of alkenes catalyzed by a chiral iridium(III) porphyrin complex
  • Article

February 2025

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7 Reads

Chem Catalysis

Sheng-Yu Li

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Shanshan Yuan

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Xiao-Ming Zhao

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[...]

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Sheng-Cai Zheng

Asymmetric allylic alkylation of indoles catalyzed by Pd/L1 complex.
Asymmetric allylic substitution reaction catalyzed by Pd/L2 complex.
Asymmetric allylic alkylation of indoles catalyzed by Pd/L2 complex.
Asymmetric alkylation of dimethyl 2‐fluoromalonate catalyzed by Pd/L3 complex.
Asymmetric allylic oxidative substitution catalyzed by Pd/L4 complex.

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Chiral Sulfoxide Ligands in Asymmetric Allylic Substitution
  • Article
  • Publisher preview available

January 2025

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12 Reads

Chiral nitrogen‐, and phosphorus‐based ligands have been extensively investigated in the asymmetric allylic reactions. However, chiral sulfoxides have not been deemed as a class of practical chiral ligands until last decade, despite several distinct advantages over traditional ligand scaffolds, such as the proximity of the chiral information to the metal center and the ability to switch between S and O coordination. This perspective collects the recent development of chiral sulfoxide ligands for asymmetric allylation since the beginning of 2013. In addition, insights into the future development of this type of promising ligand are discussed.

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Additional examples of porphyrins with chiral Cβ‐Caryl axis.
Chiral porphyrins: Literature examples and the present work. The meso‐positions include C5, C10, C15 and C20.
Derivatization of porphyrin 1 a and synthesis of Ir‐complexes. Reagents and conditions [a] RBr (8.0 equiv.), K2CO3 (8.0 equiv.), DMF (c 0.02 M), RT. [b] PhNTf2 (8.0 equiv.), Cs2CO3 (8.0 equiv.), DMF (c 0.02 M), RT. [c] Pd(OAc)2 (0.2 equiv.), Xantphos (0.6 equiv.), K3PO4 (16.0 equiv.), THF/H2O (v/v=1/1), 80 °C. [d] [Ir(COD)Cl]2 (1.5 equiv.), xylene, air, 140 °C. Abbreviation: MOE=2‐Methoxyethyl
Ir complex 3 e‐catalyzed enantioselective carbene insertion of diazo compounds 4 into C−H bond of cyclohexa‐1,4‐diene (5). All reactions were performed at 0.1 mmol scale.
Design and Synthesis of C4‐Symmetric Axially Chiral β‐Aryl Porphyrins and Application for Supporting Ir(III)‐Catalyzed Enantioselective C−H Alkylation

June 2024

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30 Reads

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4 Citations

A hitherto unknown class of C4‐symmetric Caryl−Cβ (C3, C8, C13, C18) axially chiral porphyrins has been synthesized and the application of their iridium (Ir) complexes in catalytic asymmetric C(sp³)−H functionalization is documented. Cyclotetramerization of enantioenriched axially chiral 2‐hydroxymethyl‐3‐naphthyl pyrroles under mild acidic conditions affords, after oxidation with 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ), the C4‐symmetric α,α,α,α‐atropenantiomer as an only isolable diastereomer. Both regioisomeric Ir(Por*)(CO)(Cl) complexes catalyze the carbene C−H insertion reaction affording the same enantiomer, albeit with slight difference in enantioselectivity. With the optimum Ir‐complex 3 e, the 2‐substituted arylacetic acid derivatives were generated from diazo compounds and cyclohexadiene in excellent yields and enantioselectivities.


Design and Synthesis of C₄‐Symmetric Axially Chiral β‐Aryl Porphyrins and Application for Supporting Ir(III)‐Catalyzed Enantioselective C−H Alkylation

April 2024

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2 Reads

Angewandte Chemie

A hitherto unknown class of C4‐symmetric Caryl−Cβ (C3, C8, C13, C18) axially chiral porphyrins has been synthesized and the application of their iridium (Ir) complexes in catalytic asymmetric C(sp3)−H functionalization is documented. Cyclotetramerization of enantioenriched axially chiral 2‐hydroxymethyl‐3‐naphthyl pyrroles under mild acidic conditions affords, after oxidation with 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ), the C4‐symmetric α,α,α,α‐atropenantiomer as an only isolable diastereomer. Both regioisomeric Ir(Por*)(CO)(Cl) complexes catalyze the carbene C−H insertion reaction affording the same enantiomer, albeit with slight difference in enantioselectivity. With the optimum Ir‐complex 3e, the 2‐substituted arylacetic acid derivatives were generated from diazo compounds and cyclohexadiene in excellent yields and enantioselectivities.


Rhodium-Catalyzed Tandem Asymmetric Allylic Decarboxylative Addition and Cyclization of Vinylethylene Carbonates with N-Nosylimines

February 2024

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5 Reads

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1 Citation

A enantioselective tandem transformation, concerning asymmetric allylic decarboxylative addition and cyclization of N-nosylimines with vinylethylene carbonates (VECs), in the presence of [Rh(C2H4)2Cl]2, chiral sulfoxide-N-olefin tridentate ligand has been developed. The reaction of VECs with various substituted N-nosylimines proceeded smoothly under mild conditions, providing highly functionalized oxazolidine frameworks in good to high yields with good to excellent enantioselectivity.


Figure 1. Ligands used in this reaction.
Scheme 2. Scope of the allylic substrates 2 ab . a: Reaction conditions: [Rh(C 2 H 4 ) 2 Cl] 2 (0.004 mmol), L1 (0.008 mmol), 1a (0.40 mmol), 2 (0.20 mmol), Et3N (0.30 mmol), and DCE (2.0 mL). b: Yield referred to isolated yield and ee was determined by a chiral HPLC.
Scheme 4. Possible mechanism.
Rhodium-Catalyzed Tandem Asymmetric Allylic Decarboxylative Addition and Cyclization of Vinylethylene Carbonates with N-nosylimines

January 2024

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6 Reads

A enantioselective tandem transformation concerning asymmetric allylic decarboxylative addition and cyclization of N-nosylimines with vinylethylene carbonates (VECs) in the presence of [Rh(C2H4)2Cl]2, chiral sulfoxide-N-olefin tridentate ligand has been developed. The reaction of VECs with various substituted N-nosylimines proceeded smoothly under mild conditions, giving highly functionalized oxazolidine frameworks in good to high yields with good to excellent enantioselectivity.


Ir-Catalyzed Chemo-, Regio-, and Enantioselective Allylic Enolization of 6,6-Dimethyl-3-((trimethylsilyl)oxy)cyclohex-2-en-1-one Involving Keto-Enol Isomerization

October 2022

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12 Reads

The utilization of 6,6-dimethyl-3-((trimethylsilyl)oxy)cyclohex-2-en-1-one made from an unsymmetrical 4,4-dimethylcyclohexane-1,3-dione in iridium-catalyzed allylic enolization involving keto-enol isomerization is accomplished under mild conditions. The chemoselectivity, regioselectivity, and enantioselectivity are facilitated by the quaternary carbon and adjusting the reaction conditions. This method provides the substituted 2-(but-3-en-2-yl)-3-hydroxy-6,6-dimethylcyclohex-2-en-1-ones in good to high yields with high level of chemo-, regio-, and enantioselectivities. The chiral carbon-fluorine bond formation is induced by an adjacent chiral carbon center of the allylated 3-hydroxy-6,6-dimethylcyclohex-2-en-1-one, as well.




Citations (21)


... More intriguingly, despite the wide array of studies of the click chemistry of unconjugated alkynes, very little work on the click chemistry of 1,3-diyne has been reported. Zhao et al. reported a cycloaddition of 1,3diynes with sodium azide to synthesize alkynyl-1,2,3-triazoles. 4 While this reaction with sodium azide has no consequence on regioselectivity, the use of an organic azide brings regioselectivity into play. The regioselectivity of the click reaction of a terminal alkyne can be controlled by using metal catalysts, 5−8 but the regioselectivity of internal alkynes is generally dependent on the nature of the substituents irrespective of the catalyst. ...

Reference:

Double Regioselective Thermal Azide–Alkyne Cycloaddition of 1,3-Diynes
Highly Efficient Cycloaddition Reaction of 1,3-Diynes with Sodium Azide: A New Way to 5-Substituted-4-acetylene-1 H -1,2,3-triazoles: Highly Efficient Cycloaddition Reaction of 1,3-Diynes with Sodium Azide: A New Way to 5-Substituted-4-acetylene-1 H -1,2,3-triazoles
  • Citing Article
  • June 2016

Journal of Heterocyclic Chemistry

... However, the Wilcoxon test evaluated between the PCa serum and tissue shows that miRNA 183 expression was highly significant and upregulated in tissue by 3.89-fold as compared to the serum. However, the dysregulation of miRNA is reported to be responsible for carcinogenesis in various cancers like ovarian, esophageal squamous cell, bladder, colorectal, breast, brain glioma, colon, and prostate, with upregulated expression, while other melanoma, kidney, cervical, osteosarcoma, and gastric cancers have downregulated expression [11,12]. Despite being reported as a biomarker in PCa, there are very few studies that indicate its circulating non-invasive biomarker potential in PCa biofluids. ...

Dysregulation and functional roles of miR-183-96-182 cluster in cancer cell proliferation, invasion and metastasis

Oncotarget

... The process of ovarian stimulation has an impact on the microRNA profile of the endometrium, which in turn affects the receptivity of the endometrium [148]. Previous studies showed that when women undergo ovarian stimulation, it causes their estrogen [149] and P4 amounts to become higher than normal during the late follicular stage [150] . ...

Effect of high ovarian response on the expression of endocrine gland-derived vascular endothelial growth factor (EG-VEGF) in peri-implantation endometrium in IVF women
  • Citing Article
  • August 2015

International Journal of Clinical and Experimental Pathology

... 17,18 Similar sulfonic acids g with central chirality were obtained by Zhao using asymmetric iridium-catalyzed allylation with sodium sulfite. 19 The development of chiral sulfonic acids is not limited only to central chirality. The synthesis of optically pure BINOL-derived disulfonic acids h (BINSA) was reported by Ishihara. ...

ChemInform Abstract: Asymmetric Synthesis of Allylic Sulfonic Acids: Enantio- and Regioselective Iridium-Catalyzed Allylations of Na2SO3.
  • Citing Article
  • December 2014

... Treatment with COS has been shown to induce host defense responses and delay fruit senescence (Yang et al. 2010). A low concentration of COS was shown to promote the germination of cucumber seeds, and to increase certain growth indexes (leaf area, root length) and physiological indexes (chlorophyll content and net photosynthetic rate of functional leaves) in cucumber seedlings (Ma et al. 2011). Treatment with COS at 15 g kg −1 effectively delayed the degradation of cellulose and lignin in mandarin fruit . ...

Ultrastructural Study on Induced Resistance of Cucumber Plants against Sphaerotheca fuliginea by Oligochitosan
  • Citing Article
  • March 2011

The Plant Pathology Journal

... 108 They further developed this methodology by demonstrating the enantioselective formation of analogous allyl carbamates from allyl carbonates and amines, using the released CO 2 in the presence of the same Ir complex under mild reaction conditions (Scheme 38b). 109 Later on Subsequent depolymerization of these polycarbonates using various primary or secondary amine nucleophiles afforded optically active carbamates, with the complete configuration retention of the two chiral carbon centers (Scheme 39). ...

ChemInform Abstract: Enantioselective Transformation of Allyl Carbonates into Branched Allyl Carbamates by Using Amines and Recycling CO 2 under Iridium Catalysis.
  • Citing Article
  • December 2014

... GnRHa long protocol has longer and deeper pituitary downregulation compared to GnRHa short protocol. Longer pituitary downregulation significantly increased the number of mature oocytes [27], implantation rate, the number of good-quality embryos [28], clinical pregnancy rate, and live birth rate [29]. Recent studies support that longer pituitary downregulation favors ART outcomes regardless of age or ovarian response. ...

Mini-dose GnRH-a long versus short protocol in patients ≥35 years old undergoing in vitro fertilization
  • Citing Article
  • April 2014

... Additionally, these outcomes closely matched those of Ruiz et al. (2013), who observed values of 56.5% and 63.5%, respectively, after vitrifying mature alpaca oocytes for 45 and 30 seconds using 30% EG. However, Wang et al. (2014) found that combining 30% EG with 20% FBS for 45 seconds had better outcomes 93.6%. While in camelids, EG has been effectively applied to the vitrification of alpaca oocytes and embryos (Ruiz et al., 2013 andVivanco-Mackie, 2013), llama (Aller et al., 2002), and dromedary (Nowshari, 2005). ...

The effect of minimal concentration of ethylene glycol (EG) combined with polyvinylpyrrolidone (PVP) on mouse oocyte survival and subsequent embryonic development following vitrification
  • Citing Article
  • November 2013

Journal of Assisted Reproduction and Genetics

... Catalysts 2022, 12 Due to the importance of these moieties, different strategies for obtaining them have been developed in the past (Scheme 1). Zhao and coworkers published the transition metal catalyzed allylic substitution with sodium benzotriazolide [13,14]. Despite the excellent enantioselectivities in some cases, the method lacks regioselectivity and requires deprotonation of the triazole in a previous step. ...

ChemInform Abstract: Enantioselective Iridium-Catalyzed Allylation of Sodium Benzotriazolide: An Efficient Way to Chiral Allylbenzotriazoles.
  • Citing Article
  • December 2012

Tetrahedron Letters

... To overcome this challenge, alkyl-and aryl sodium thiolates have been applied in the Ir-catalyzed reaction of linear allylic carbonates to give the corresponding allylic sulfides in good yields and selectivities. [33][34][35] The use of branched, aryl-substituted allylic alcohols in the presence of dibutyl phosphoric acid has been recently reported in the Ir-catalyzed asymmetric thioetherification. [36] Reaction of aliphatic and electron-deficient allylic alcohols by this method, [36] however, underwent kinetic resolution. ...

ChemInform Abstract: Iridium-Catalyzed Enantioselective Allylation of Sodium 2-Aminobenzenethiolate: An Access to Chiral Benzo-Fused N,S-Heterocycles.
  • Citing Article
  • November 2012

ChemInform