Abstract
Thiophenol was discovered to form an EDA complex with iodobenzene through halogen bonding interactions upon treatment with KOH. A direct photochemical thiolation of C(sp3)–H bond-containing etheric, allylic, and benzylic substrates with thiophenol was developed. The reaction proceeded on the basis of the in situ generation of a thiyl radical and aryl radical through single electron transfer between the photoexcited thiophenolate anion and aryl iodide EDA complex. Then a C(sp3) centred-radical was formed by aryl radical-mediated hydrogen atom transfer and the thiolation products were delivered via a radical–radical cross-coupling with the thiyl radical.
Highlights
A visible light-induced photoreaction generates electronically excited open-shell species which expand novel and unique organic chemistry
Miyake reported that the thiophenolate anion formed an electron donor–acceptor (EDA) complex via p–p interactions with aryl halides in the presence of Cs2CO3 and was excited under visible light irradiation (Scheme 1a)
We discovered that when thiophenol 1 was treated with KOH instead of Cs2CO3 in THF, the spectrum of the thiophenolate anion showed a signi cant bathochromic shi with absorption tailing to the 400–450 nm region (Fig. 1a, red line)
Summary
A visible light-induced photoreaction generates electronically excited open-shell species which expand novel and unique organic chemistry. It is discovered that there is a region of positive electrostatic potential surrounded by negative electrostatic potential, termed a “shole”, on the outermost portions of the halogen atom surface.. It is discovered that there is a region of positive electrostatic potential surrounded by negative electrostatic potential, termed a “shole”, on the outermost portions of the halogen atom surface.6 This electron de ciency area is responsible for the formation of. Organosulfur compounds have received great attention in the elds of pharmaceutical chemistry, chemical biology, and advanced functional materials.9 Among those established synthetic protocols, the methods for formation of C–S bonds via functionalization of the C–H bond mainly focused on the C(sp2)–H bonds.. Both the allylic radical and thiyl radical were generated on the surface of photocatalyst quantum dots via hydrogen evolution followed by direct radical–radical cross-coupling to afford the allylic C(sp3)– H thiolation products Organosulfur compounds have received great attention in the elds of pharmaceutical chemistry, chemical biology, and advanced functional materials. Among those established synthetic protocols, the methods for formation of C–S bonds via functionalization of the C–H bond mainly focused on the C(sp2)–H bonds. The thiolation of C(sp3)–H bonds normally relied on the cross-coupling of oxidatively generated radicals with disul des or in situ generated disul des. The disul des were applied to the nickel-catalyzed thiolation of b-methyl C(sp3)–H bonds of aliphatic carboxamides. Very recently, Wu reported the rst direct use of thiophenol for the allylic C(sp3)– H thiolation. Under visible light irradiation, both the allylic radical and thiyl radical were generated on the surface of photocatalyst quantum dots via hydrogen evolution followed by direct radical–radical cross-coupling to afford the allylic C(sp3)– H thiolation products
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