Seminar

Seminar

Access Molecular Complexity by Breaking Symmetry of Dicarbonyl Compounds

  • POSTED DATE : 2023-06-09
  • WRITER : 화학과
  • HIT : 1998
  • DATE : 2023년 6월 14일(수)오전 10시 30분
  • PLACE : 330226호실

화학과 특별 세미나가 다음주 수요일(6월 14일) 오전 10시 30분에 개최됩니다.

많은 참여 부탁드립니다.


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제  목 : Access Molecular Complexity by Breaking Symmetry of Dicarbonyl Compounds

연  사 : Prof. Zhongxing Huang(University of Hong Kong)
일  시 : 
2023년 6월 14일(수)오전 10시 30분

장  소 : 화학관 2층 330226호실

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Access Molecular Complexity by Breaking Symmetry of Dicarbonyl Compounds

Zhongxing Huang

University of Hong Kong

huangzx@hku.hk

 

 

1,3-Dicarbonyl compounds represent a prominent family of structures that are easily available and can provide rapid access to complex molecules. When doubly substituted, these compounds can be rapidly converted to valuable tetrasubstituted stereocenters via asymmetric transformations. Here, we report a prolinol- or pipecolinol-derived tetradentate ligand scaffold that can house two zinc centers or a single magnesium atom to desymmetrize malonic esters and 1,3-diketones. The reductive desymmetrization of disubstituted malonic ester via hydrosilylation has enabled the stereoselective synthesis of various enantioenriched building blocks, including quaternary stereocenters, tertiary alkyl halides, α-tertiary amines, and tertiary alcohols. Consequently, novel and expeditious approaches to bioactive natural metabolites, such as 2-dechlorohalomon, conagenin, and yezo’otogirins, were devised. Meanwhile, the magnesium-catalyzed desymmetric cyanosilylation of acyclic 1,3-diketones using the same ligand scaffolds afforded two vicinal tetrasubstituted carbons. The polyfunctionalized nature of the chiral cyanohydrin products can be used to access molecules of higher complexity, particularly those with consecutive stereocenters.




References:

(1) Xu, Pengwei.; Huang, Z.*, Nat. Chem. 2021, 13, 634.

(2) Zheng, Y.; Zhang, S.; Low, K.-H.; Zi, W.; Huang, Z.*, J. Am. Chem. Soc. 2022, 144, 1951-1961.

(3) Xu, Pengwei.; Liu, S.; Huang, Z.*, J. Am. Chem. Soc. 2022, 144, 6918-6927.

(4) Xu, Pan.; Shen, C.; Xu, A.; Low, K.-H.; Huang, Z.*, Angew. Chem. Int. Ed. 2022, 61, e202208443.

(5) Liu, Haichao; Lau, H. M.; Xu, P.; Chan, T. H.; Huang, Z.*, Nat. Commun. 2022, 13, 4759.