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Previously unobserved (carbamoyl)disulfanyl chlorides were prepared by (i) addition of limiting aromatic secondary amine to (chlorocarbonyl)disulfanyl chloride; (ii) Harris reactions of sulfur dichloride with appropriate O-alkyl N-methyl-N-arylthiocarbamates; and (iii) regiospecific chlorolysis of bis(N-methyl-N-arylcarbamoyl)disulfanes. The newly synthesized unstable species were observed in situ by 1H NMR and were trapped with alkenes, thiocarbamates, and thiols using methods precedented by the chemistry of analogous (carbamoyl)sulfenyl chlorides. Furthermore, each of the trapped products was synthesized by an alternate route, reinforcing conclusions about their structures. While (N-methyl-N-phenylcarbamoyl)disulfanyl chloride was unstable and decomposed quickly or cyclized intramolecularly, introduction of the N,2,6-trimethylphenyl moiety led to significantly improved stability. As part of this study, an interesting, unexpectedly stable 1,2,4-dithiazinone was discovered and its structure was established by X-ray crystallography. The new heterocycle, with its twisted out-of-plane disulfide bond in a six-membered ring, readily donated a sulfur atom to triphenylphosphine; this reaction resulted in the formation of triphenylphosphine sulfide, along with the corresponding highly stable heterocycle in which the single sulfur that remains is part of a planar five-membered ring, fused to a co-planar aryl moiety.
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Visible Light-Assisted Ring-Opening of Cyclic Ethers with Carboxylic Acids Mediated by Triphenylphosphine and N-Halosuccinimides
The ring-opening of cyclic ethers (epoxide, oxetane, THF, and THP) by carboxylic acids was achieved by using N-iodosuccinimide (NIS) or N-bromosuccinimide (NBS) and triphenylphosphine under the irradiation of blue light. The corresponding omega-haloalkyl carboxylates were obtained under mild reaction conditions. The reaction is believed to work through a halogen bond complex between NIS (or NBS) and triphenylphosphine, which, upon irradiation with blue light, produces the key phosphine radical cation intermediate that initiates the ring-opening reactions.
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- Award ID(s):
- 1664278
- PAR ID:
- 10483869
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- Organic Letters
- ISSN:
- 1523-7060
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acs.orglett.3c03805
