1. Yadong Gao, Chao Yang, Sonlin Bai, Xiaolei Liu, Qingcui Wu, Chao jiang*, Xiangbing Qi*, “Visible-light-induced Nickel-catalyzed Cross-coupling with Alkylzirconocenes from Unactivated Alkenes” Chem, Dec.12, 2019.
Significance:“First alkylzirconocenes in light-induced cross-coupling; Chain walking and cross-coupling cascade for remote functionalization of alkenes;Convergent functionalization of alkene mixtures with broad substrate scope; Novel radical coupling mechanism; First AlkyZr radical precursor! Simple visible-light energy source!“
2. Shufang Zhao; Wenchao Ma; Mumtaz Yasir; Xinli Zhou; Jintang Cheng; Chao Jiang* “Palladium-Catalyzed C2-Selective Alkynylation of Indoles with Bromoalkynes” ChemistrySelect 2018,3, 13319– 13322.
Significance:The Pd(II) catalyzed direct C2 alkynylation of indoles bearing N-2-pyrimidyl or N-2-pyridinyl moiety as a site-specific directing group was developed with alkynyl halide. A highly regioselective manner can be achieved on a range of indole substrates with excellent functional group tolerance.
3. Qiumei Wang, Chao Yang, Chao Jiang* “Visible-light-promoted radical acylation/cyclization of alkynoates with aldehydes for the synthesis of 3-acylcoumarins”Org. Biomol. Chem.,2018,16, 8196-8204.
Significance: A new, efficient, and atom-economic visible-light-promoted radical acylation/cyclization of alkynoates with aldehydes was developed for the synthesis of 3-acylcoumarins. The reaction undergoes a domino radical addition/5-exo cyclization, and ester migration to afford the product in moderate to good yields with wide functional group tolerance. The significant feature of this new method is the excellent tolerance of aliphatic aldehydes, which leads to the efficient synthesis of aliphatic 3-acylcoumarins.
4. Jingjing Fu; Yadong Gao; Xiangbing Qi; Chao Jiang* “Synthesis of Polysubstituted Pyridines and Indoles by a Palladium-Catalyzed Catellani-type Alkylation-Alkenylation Sequence”ChemistrySelect2018,3, 10164– 10168.
Significance: The C−H functionalization of heterocycles has attracted extensive attention recently due to the ubiquity of substituted heterocycles in natural products, drugs, and other bioactive molecules. The Catellani‐type C−H functionalization, which is a palladium‐catalyzed and norbornene‐mediated coupling process, can properly overcome the metal poisoning between hetero atoms and metal catalyst.
5. Chen Yang, Chong Zhang, Zhansheng Zheng, Chao Jiang, Jun Luo, Yang Du, Bingcheng Hu, Chengguo Sun, Karl O. Christe “Synthesis and Characterization of cyclo-Pentazolate Salts of NH4+, NH3OH+, N2H5+, C(NH2)3+, and N(CH3)4+”J. Am. Chem. Soc.,2018,140, 16488.
Significance: A breakthrough in polynitrogen chemistry was recently achieved by our bulk synthesis of (N5)6(H3O)3(NH4)4Cl in which the cyclo-pentazolate anions were stabilized extensively by hydrogen bridges with the NH4+ and OH3+ cations.
6. Chao Yang; Jing Wang; Jianhua Li; Wenchao Ma; Kun An; Wei He; Chao Jiang * “Visible‐Light Induced Radical Silylation for the Synthesis of Dibenzosiloles via Dehydrogenative Cyclization”Adv. Synth. Catal.,2018,360, 3049–3054.
Significance:A visible‐light induced radical silylation to dibenzosiloles from biarylhydrosilanes is described. The products were obtained in satisfactory yields under mild and water/air compatible conditions, providing an efficient and practical method for the synthesis of difunctionalized siloles by using a cheap organic dye photocatalyst.
7. Chao Jiang, Lei Zhang, Chengguo Sun, Chong Zhang, Chen Yang, Jun Chen, Bingcheng Hu* “Response to Comment on “Synthesis and characterization of the pentazolate anion cyclo-N5– in (N5)6(H3O)3(NH4)4Cl”Science,2018,359, aas8953.
Significance: Huang and Xu argue that the cyclo-N5- ion in (N5)6(H3O)3(NH4)4Cl we described in our report is theoretically unfavorable and is instead protonated. Their conclusion is invalid, as they use an improper method to assess the proton transfer in a solid crystal structure. We present an in-depth experimental and theoretical analysis of (N5)6(H3O)3(NH4)4Cl that supports the results in the original paper.
8. Chengguo Sun, Chong Zhang, Chao Jiang, Chen Yang, Yang Du, Yue Zhao, Bingcheng Hu, Zhansheng Zheng, Karl O Christe* “Synthesis of AgN5 and its extended 3D energetic framework”Nature Commun.,2018,9:1269,
Significance: we report a solvent-free pentazolate complex, AgN5, and a 3D energetic-framework, [Ag(NH3)2]+[Ag3(N5)4]-, constructed from silver and cyclo-N5-. The complexes are stable up to 90 °C and only Ag and N2 are observed as the final decomposition products. Efforts to isolate pure AgN5 were unsuccessful due to partial photolytical and/or thermal-decomposition to AgN3. Convincing evidence for the formation of AgN5 as the original reaction product is presented. The isolation of a cyclo-N5- complex, devoid of stabilizing molecules and ions, such as H2O, H3O+, and NH4+, constitutes a major advance in pentazole chemistry.
9. Daoquan Tu, Jun Luo, Chao Jiang* “Copper-mediated domino C–H iodination and nitration of indoles”Chem. Commun.,2018,54, 2514–2517.
Significance:An efficient and cost-effective copper-mediated aerobic oxidative C–H iodination and nitration of indoles via double C–H functionalization is reported. The domino process proceeds smoothly under mild aerobic conditions to give 3-iodo-2-nitroindoles in one step with high regioselectivity and a broad substrate scope. The mechanism of the iodination step is proposed to proceed via a Cu(III)-iodide species that undergoes electrophilic addition at the C3 position of the indole motif.
10. Wanting Zeng, Moldir Nukeyeva, Qiumei Wang, Chao Jiang *“Synthesis of Unnatural α‑Amino Acid Derivatives via Selective o-C-H Functionalization”Org. Biomol. Chem.,2018,16, 598–608.
Significance:Pd-Catalyzed o-C–H functionalization of α-phenylglycine, 4-hydroxyphenylglycine and phenylalanine using picolinamide as a directing group is reported. We have developed different protocols for the arylation, alkylation, alkynylation, halogenation, alkoxylation, and acyloxylation of these amino acids. The reactions exhibit high selectivity, broad substrate scope, and compatibility with different functional groups in moderate to high yields.
11. Yadong Gao, Wangying Zhu, Long Yin, Bo Dong, Jingjing Fu, Zhiwen Ye, Fengtian Xue, Chao Jiang*“Palladium-catalyzed direct C2-arylation of free (N-H) indoles via norbornene-mediated regioselective C-H activation”Tetrahedron Lett.,2017,58, 2213–2216.
Significance:A palladium-catalyzed direct C2-arylation reaction of free (N-H) indoles has been developed. This reaction relies on a norbornene-mediated C-H activation process on the indole ring, which features high regioselectivity and excellent functional group tolerance.
12. Dongdong Liang, Deanna Sersen, Chao Yang, Jeffrey R. Deschamps, Gregory H. Imler, Chao Jiang, Fengtian Xue.* “One-Pot Sequential Reaction to 2-Substituted-Phenanthridinones from N-Methoxybenzamides”Org. Biomol. Chem.,2017,15, 4390–4398.
Significance The sequential use of a hypervalent iodine reagent leads to the one-pot synthesis of 2-bromo/chloro-phenanthridinones via an amidation of arenes followed by a regioselective halogenation reaction. These consecutive C–H functionalization reactions can be used efficiently to construct 2-substituted-phenanthridinones at room temperature with good to high yields. Application of the current method is highlighted by the concise synthesis of the natural product PJ34.