Biomolecule-Compatible Dehydrogenative Chan-Lam Coupling of Free Sulfilimines

Meng, Tingting1,2,3; Wells, Lucille A.4; Wang, Tianxin2,3; Wang, Jinyu2,3; Zhang, Shishuo2,3; Wang, Jie2,3; Kozlowski, Marisa C.4; Jia, Tiezheng2,3,5

2022-06-01

10.1021/jacs.2c04627

Journal of the American Chemical Society   Impact Factor & Quartile

0002-7863

1520-5126

Inspired by the discovery of a S=N bond in the collagen IV network and its essential role in stabilizing basement membranes, sulfilimines have drawn much attention in the fields of chemistry and biology. However, their further uptake is hindered by the lack of mild, efficient, and environmentally benign protocols by which sulfilimines can be constructed under biomolecule-compatible conditions. Here, we report a terminal oxidant-free copper-catalyzed dehydrogenative Chan-Lam coupling of free diaryl sulfilimines with arylboronic acids with excellent chemoselectivity and broad substrate compatibility. The mild reaction conditions and biomoleculecompatible nature allow the employment of this protocol in the late-stage functionalization of complex peptides, and more importantly, as an effective bioconjugation method as showcased in a model protein. A combined experimental and computational mechanistic investigation reveals that an inner-sphere electrontransfer process circumvents the sacrificial oxidant employed in traditional Chan-Lam coupling reactions. An energetically viable concerted pathway was located wherein a copper hydride facilitates hydrogen-atom abstraction from the isopropanol solvent to produce dihydrogen via a four-membered transition state.

SCI ; EI

English

NI Journal Papers

Corresponding

Guangdong-Joint Foundation of Shenzhen[2021B1515120046] ; Natural Science Foundation of Guangdong Province[2022A1515011770] ; Shenzhen Nobel Prize Scientists Laboratory Project[C17783101] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002] ; NIH[R35 GM131902] ; XSEDE[TG-CHE120052]

Chemistry

Chemistry, Multidisciplinary

WOS:000823202700001

AMER CHEMICAL SOC

20223012417806

Atoms ; Chemical bonds ; Copper compounds ; Electron transport properties ; Oxidants ; Proteins

Biology:461.9 ; Biochemistry:801.2 ; Physical Chemistry:801.4 ; Chemical Agents and Basic Industrial Chemicals:803 ; Organic Compounds:804.1 ; Atomic and Molecular Physics:931.3

Web of Science

1.Harbin Inst Technol, Sch Chem & Chem Engn, Harbin 150001, Peoples R China
2.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Dept Chem, Shenzhen 518055, Guangdong, Peoples R China
3.Southern Univ Sci & Technol, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Guangdong, Peoples R China
4.Univ Penn, Dept Chem, Roy & Diana Vagelos Labs, Penn Merck Lab High Throughput Experimentat, Philadelphia, PA 19104 USA
5.Nankai Univ, State Key Lab Elemento Organ Chem, Tianjin 300071, Peoples R China

Meng, Tingting,Wells, Lucille A.,Wang, Tianxin,et al. Biomolecule-Compatible Dehydrogenative Chan-Lam Coupling of Free Sulfilimines[J]. Journal of the American Chemical Society,2022,144:12476-12487.

Meng, Tingting.,Wells, Lucille A..,Wang, Tianxin.,Wang, Jinyu.,Zhang, Shishuo.,...&Jia, Tiezheng.(2022).Biomolecule-Compatible Dehydrogenative Chan-Lam Coupling of Free Sulfilimines.Journal of the American Chemical Society,144,12476-12487.

Meng, Tingting,et al."Biomolecule-Compatible Dehydrogenative Chan-Lam Coupling of Free Sulfilimines".Journal of the American Chemical Society 144(2022):12476-12487.