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Catalyst-Dependent Stereospecific [3,3]-Sigmatropic Rearrangement of Sulfoxide-Ynamides: Divergent Synthesis of Chiral Medium-Sized N,S-Heterocycles.
Angew Chem Int Ed Engl. 2022 07 11; 61(28):e202204603.AC

Abstract

Medium-sized N,S-heterocycles have received tremendous interest due to their biological activities and potential medical applications. However, asymmetric synthesis of these compounds are extremely rare. Described herein is a catalyst-dependent [3,3]-sigmatropic rearrangement of sulfoxide-ynamides, enabling divergent and atom-economic synthesis of a series of valuable medium-sized N,S-heterocycles in moderate to good yields with broad substrate scope. Importantly, excellent enantioselectivities have been achieved via an unprecedented chirality-transfer. Moreover, theoretical calculations are employed to elucidate the origins of the catalyst-dependent stereospecific [3,3]-rearrangement.

Authors+Show Affiliations

State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China. State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, 200032, China.

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

35474275

Citation

Zhu, Guang-Yu, et al. "Catalyst-Dependent Stereospecific [3,3]-Sigmatropic Rearrangement of Sulfoxide-Ynamides: Divergent Synthesis of Chiral Medium-Sized N,S-Heterocycles." Angewandte Chemie (International Ed. in English), vol. 61, no. 28, 2022, pp. e202204603.
Zhu GY, Zhou JJ, Liu LG, et al. Catalyst-Dependent Stereospecific [3,3]-Sigmatropic Rearrangement of Sulfoxide-Ynamides: Divergent Synthesis of Chiral Medium-Sized N,S-Heterocycles. Angew Chem Int Ed Engl. 2022;61(28):e202204603.
Zhu, G. Y., Zhou, J. J., Liu, L. G., Li, X., Zhu, X. Q., Lu, X., Zhou, J. M., & Ye, L. W. (2022). Catalyst-Dependent Stereospecific [3,3]-Sigmatropic Rearrangement of Sulfoxide-Ynamides: Divergent Synthesis of Chiral Medium-Sized N,S-Heterocycles. Angewandte Chemie (International Ed. in English), 61(28), e202204603. https://doi.org/10.1002/anie.202204603
Zhu GY, et al. Catalyst-Dependent Stereospecific [3,3]-Sigmatropic Rearrangement of Sulfoxide-Ynamides: Divergent Synthesis of Chiral Medium-Sized N,S-Heterocycles. Angew Chem Int Ed Engl. 2022 07 11;61(28):e202204603. PubMed PMID: 35474275.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Catalyst-Dependent Stereospecific [3,3]-Sigmatropic Rearrangement of Sulfoxide-Ynamides: Divergent Synthesis of Chiral Medium-Sized N,S-Heterocycles. AU - Zhu,Guang-Yu, AU - Zhou,Ji-Jia, AU - Liu,Li-Gao, AU - Li,Xiao, AU - Zhu,Xin-Qi, AU - Lu,Xin, AU - Zhou,Jin-Mei, AU - Ye,Long-Wu, Y1 - 2022/05/09/ PY - 2022/03/29/received PY - 2022/4/28/pubmed PY - 2022/7/8/medline PY - 2022/4/27/entrez KW - Alkynes KW - Asymmetric Synthesis KW - Cyclization KW - Heterocycles KW - [3,3]-Rearrangement SP - e202204603 EP - e202204603 JF - Angewandte Chemie (International ed. in English) JO - Angew Chem Int Ed Engl VL - 61 IS - 28 N2 - Medium-sized N,S-heterocycles have received tremendous interest due to their biological activities and potential medical applications. However, asymmetric synthesis of these compounds are extremely rare. Described herein is a catalyst-dependent [3,3]-sigmatropic rearrangement of sulfoxide-ynamides, enabling divergent and atom-economic synthesis of a series of valuable medium-sized N,S-heterocycles in moderate to good yields with broad substrate scope. Importantly, excellent enantioselectivities have been achieved via an unprecedented chirality-transfer. Moreover, theoretical calculations are employed to elucidate the origins of the catalyst-dependent stereospecific [3,3]-rearrangement. SN - 1521-3773 UR - https://www.unboundmedicine.com/medline/citation/35474275/Catalyst_Dependent_Stereospecific_[33]_Sigmatropic_Rearrangement_of_Sulfoxide_Ynamides:_Divergent_Synthesis_of_Chiral_Medium_Sized_NS_Heterocycles_ DB - PRIME DP - Unbound Medicine ER -