Article
Chemistry, Multidisciplinary
Yang-Bo Chen, Li-Gao Liu, Can-Ming Chen, Yi-Xi Liu, Bo Zhou, Xin Lu, Zhou Xu, Long-Wu Ye
Summary: In this study, a copper-catalyzed atroposelective diyne cyclization was disclosed for the synthesis of a range of axially chiral arylpyrrole biaryls with good to excellent yields and enantioselectivities. This method represents the first synthesis of mono-substituted 3-arylpyrrole atropisomers and the first example of atroposelective diyne cyclization and atropisomer construction using vinyl cations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Feng-Lin Hong, Chong-Yang Shi, Pan Hong, Tong-Yi Zhai, Xin-Qi Zhu, Xin Lu, Long-Wu Ye
Summary: In this study, a copper-catalyzed asymmetric cascade cyclization/[1,2]-Stevens-type rearrangement was reported to efficiently assemble a variety of valuable chiral chromeno[3,4-c]pyrroles bearing a quaternary carbon stereocenter with generally moderate to good yields and excellent enantioselectivities (up to 99% ee). Notably, this protocol represents the first example of catalytic asymmetric [1,2]-Stevens-type rearrangement based on alkynes and the first asymmetric formal carbene insertion into the Si-O bond.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Lin-Jun Qi, Cui-Ting Li, Zheng-Qi Huang, Jia-Tian Jiang, Xin-Qi Zhu, Xin Lu, Long-Wu Ye
Summary: The study presents a novel copper-catalyzed asymmetric formal annulation reaction, which can synthesize a range of chiral oxygen-heterocycles via carbonyl ylides with excellent enantioselectivity and yields.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Applied
Anna Gulevskaya, Daria Tonkoglazova
Summary: Helicenes are polycyclic aromatic molecules with unique structures and properties. They have been widely applied in material science, nanoscience, and other fields. However, synthesizing helicenes remains a challenge, and alkyne cyclizations show great potential as a method. This review focuses on the development and applications of alkyne-based syntheses of carbo- and heterohelicenes.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Peng-Fei Chen, Bo Zhou, Peng Wu, Binju Wang, Long-Wu Ye
Summary: A novel Brønsted acid catalyzed intramolecular hydroalkoxylation/Claisen rearrangement is described for the synthesis of valuable spirolactams from readily available ynamides with good yields, diastereoselectivities, and broad substrate scope. An unexpected dearomatization of nonactivated arenes and heteroaromatic compounds occurs in this reaction. Furthermore, an asymmetric version of this reaction was achieved through efficient kinetic resolution by chiral phosphoric acid catalysis, with theoretical calculations showing a preference for the [3,3]-rearrangement over the [1,3]-rearrangement.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Ban Van Phuc, Ha Nam Do, Nguyen Minh Quan, Nguyen Ngoc Tuan, Nguyen Quang An, Nguyen Van Tuyen, Hoang Le Tuan Anh, Tran Quang Hung, Tuan Thanh Dang, Peter Langer
Summary: Two efficient methods for synthesizing beta- and delta-carbolines from 3,4-dibromopyridine are reported, involving Cu-catalyzed double C-N coupling reactions and subsequent Pd-catalyzed C-N coupling with amines.
Article
Chemistry, Multidisciplinary
Xiao-Wen Zhang, Ming-Hui Zhu, Hai-Xiang Zeng, Qi-Yang Li, Wen-Bo Liu
Summary: This study presents a highly enantioselective NiH-catalyzed hydrocyclization of alkynones, yielding an array of enantioenriched heterocyclic tertiary allylic alcohols. The choice of precatalysts significantly influences the selectivity of the products, with yields reaching up to 81%.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Christian Frabitore, Tom Livinghouse
Summary: This article presents a novel synthetic method for the production of saturated N-heterocyclic pharmacophore motifs, utilizing N,N-dimethylhydrazinoalkenes and diethylzinc followed by a Cu(I)-catalyzed cross-coupling reaction with 1-bromoalkynes to afford piperidines and pyrrolidines. The synthesis tolerates heteroatom-bearing alkynes and, unexpectedly, the use of ethyl propiolate as the trapping electrophile leads to selective N-functionalization with the formation of vinylogous urethanes. Alternative Cu(I) complexes were also evaluated as potential catalysts. This synthetic protocol can be easily scaled up for preparative purposes.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Vibha V. Kanale, Christopher Uyeda
Summary: Cobalt catalysts facilitate highly enantioselective ring-opening reactions of 2,5-dihydrofurans using vinylidenes. The resulting products are acyclic organozinc compounds, capable of further functionalization with an electrophile. The proposed mechanism involves the formation of a cobalt vinylidene species that adds to the alkene via a [2+2]-cycloaddition pathway, followed by ring-opening through outer-sphere & beta;-O elimination assisted by a ZnX2 Lewis acid. DFT models explain the observed stereochemical outcome by suppressing competing inner-sphere syn & beta;-H and & beta;-O elimination pathways due to the geometric constraints of the metallacycle intermediate. Cobalt catalysts also promote enantioselective ring-opening reactions of unstrained heterocycles via reductive addition of 1,1-dichloroalkenes. The resulting products are acyclic homoallylic alcohols with a vinylzinc motif, which can be further modified with an electrophile. Mechanistic studies suggest that the ring-opening occurs through outer-sphere & beta;-O elimination facilitated by a Zn(II) Lewis acid.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Marian Blanco Ponce, Maria Ines Mangione, Robinson Hermosilla Espinosa, Eugenio Torres Rodriguez, Peter Ehlers, Peter Langer
Summary: A variety of thieno[3,2-f]isoquinolines were synthesized by combining Pd catalysed cross-coupling reactions with Bronsted acid mediated cycloisomerisations, with high selectivity towards various functional groups. In addition, benzothieno[3,2-f]isoquinolines were prepared, representing a new heterocyclic core structure. The optical properties of selected compounds were studied, and solvatochromism characteristic of intramolecular charge transfer was observed for one compound with a push-pull structure.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Chemistry, Organic
Pascal Matton, Steve Huvelle, Mansour Haddad, Phannarath Phansavath, Virginie Ratovelomanana-Vidal
Summary: Metal-catalyzed [2+2+2] cycloaddition is a powerful method for the rapid construction of functionalized 6-membered carbo- and heterocycles with high functional group tolerance. The reaction is usually regio- and chemoselective, but challenges remain for intermolecular reactions involving multiple alkynes.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Multidisciplinary
Tobias Wagener, Lukas Lueckemeier, Constantin G. Daniliuc, Frank Glorius
Summary: This study successfully demonstrates the synthesis of sought-after, enantioenriched delta-lactams through an interrupted hydrogenation mechanism using oxazolidinone-substituted pyridines and water.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Melania Gomez-Martinez, Maria del Carmen Perez-Aguilar, Dariusz G. Piekarski, Constantin G. Daniliuc, Olga Garcia Mancheno
Summary: An enantioselective anion-binding organocatalytic approach using versatile N,N-dialkylhydrazones as polarity-reversed nucleophiles is presented. A highly ordered hydrogen-bond network was envisioned between a CF3-substituted triazole-based multidentate HB-donor catalyst, the ionic substrate, and the hydrazone in a supramolecular chiral ion-pair complex. Experimental and computational studies supported the formation of this network, showing the crucial role of the anion as a template unit. The asymmetric reaction provided highly enantiomerically enriched hydrazones that could be further derivatized to value-added compounds with up to three stereocenters.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Guang-Yu Zhu, Ji-Jia Zhou, Li-Gao Liu, Xiao Li, Xin-Qi Zhu, Xin Lu, Jin-Mei Zhou, Long-Wu Ye
Summary: A catalyst-dependent [3,3]-sigmatropic rearrangement of sulfoxide-ynamides has been described, enabling the divergent and atom-economic synthesis of valuable medium-sized N,S-heterocycles with moderate to good yields and broad substrate scope. Excellent enantioselectivities have been achieved via an unprecedented chirality-transfer. Theoretical calculations have been employed to elucidate the origins of the catalyst-dependent stereospecific [3,3]-rearrangement.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Hanying Diao, Li Liu, Jin Wang, Yanfei Lin, Xiangyuan Zhao, Heyang Zeng, Senlei Shi, Wei Gao, Long Yang, Guanben Du, Lianpeng Zhang
Summary: A convenient and efficient one pot synthesis method for polysubstituted (Z)-halobenzo[c,d]indoles has been developed using CuCl2 and CuBr2 as halogenated reagents. The protocol allows for the synthesis of both (Z)-chloro and bromobenzo[c,d]indole derivatives in moderate to good yields using copper halide-promoted intramolecular cis-addition annulation reactions. A novel fluorescent molecule with aggregation-induced emission (AIE) properties was constructed via Suzuki coupling reaction, and its optical properties were investigated, showing potential applications as optoelectronic conjugated materials.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)