Synthesis of S‐Trifluoromethyl S‐Arylsulfoximine Thioglycosides through Pd‐Catalyzed Migita Cross‐Coupling

Abstract

A general protocol for the synthesis of S-trifluoromethyl S-arylsulfoximine thioglycosides has been reported. This protocol is based on a Pd-catalyzed Migita cross-coupling between o-iodo S-trifluoromethyl S-arylsulfoximines and a broad range of 1-thiosugars. This method gives access to a series of [a

Dual Photocatalysis for the Straightforward Coupling of Thiosugars and Arylsulfoximines: Towards Unprecedented Cyclic Heteroatomic Structures

“…On the other hand, The best conditions identified (entry 7), we then started their evaluation with five thiosugars 7 a-e and eight sulfoximines: 3 a-b, 6 a-b, 8 a-b, and two others already prepared and used in our laboratory, N-methyl S-trifluoromethyl Sphenylsulfoximine 10, and S-methyl S-phenylsulfoximine 11. [8] We initiated the study with the S-methyl and S-trifluoromethyl sulfoximines in order to compare the dual catalysis to palladium chemistry (Scheme 3). [8] We were pleased to obtain comparable to somewhat better yields in the CF 3 series and a significantly improved yield for the S-methyl compound 9 g (58 % vs 49 % yield with Pd-catalysis).…”

“…High resolution mass spectrometry (HRMS) was recorded on a Mass Spectrometer XEVO‐QTOF in the Institute Lavoisier of Versailles – University of Versailles‐Saint‐Quentin. Thiosugars were synthesized according to literature protocols [8] . 2‐iodosulfoximine 8 a and 2‐bromosulfoximine 8 b were prepared as reported [7a] .…”

“…Thiosugars were synthesized according to literature protocols. [8] 2iodosulfoximine 8 a and 2-bromosulfoximine 8 b were prepared as reported. [7a] Molecular sieves were dried at 200 °C under stirring and vacuum overnight and stored under argon for several weeks.…”

“…2). [8] This methodology although efficient, possesses some drawbacks and limitations, the most compelling of which are the high load (10 mol%) of an expensive and rare metal-catalyst, the heating of the mixture and the need for an iodine atom on the aromatic ring. No crosscoupling occurred between thioglycosides and bromoaryl derivatives as substrates.…”

One-Pot Synthesis of N-Iodo Sulfoximines from Sulfides

“…These compounds are of great importance as ligands, auxiliaries, and catalysts, e.g., in asymmetric synthesis and catalysis. , Recently, a large number of reports on their synthesis and transformations have appeared in the literature, − including halo- and chalcogenations. Sulfoximines undergo chlorinations with NCS (Figure a), brominations with NBS (Figure b), trifluoromethylthiolations with AgSCF 3 (Figure c), trifluoromethylations (Figure d), − halocyclizations with (diacetoxyiodo)­benzene (DIB)/KI (Figure e), reactions with (DIB)/I 2 under visible light (Figure f), chlorinations and N -sulfonylations in the presence of I 2 /H 2 O 2 (Figure g), for example.…”