Tributylstannane-mediated cyclization of thionocarboxylic acid derivatives
Abstract
Cyclization reactions of various thionoesters and thioamides involving the addition of tri-n-butylstannyl radical to a thiocarbonyl group and intramolecular addition of the resulting radical to a carbon-carbon multiple bond was studied. Dithiocarbonate and (imidazolyl)thiocarbonyl derivatives of homoallylic alcohols gave α-substituted γ-thionobutyrolactones. The reaction is highly dependent on the substitution pattern on the double bond, a high yield of cyclic products being obtained only when the double bond is activated and unhindered. (Z)-4-Phenylbut-3-enyl thionobenzoate afforded 4,5-dihydro-2-phenyl-3-benzylfuran in low yield. In reactions involving a thioamide group, good yields of cyclic products were obtained only from compounds in which the electron density on the nitrogen atom is decreased by an electron attracting group. Cyclization of 1-((E)-4-phenylbut-3-en-1-yl)-5-thioxopyrrolidin-2-one (23) afforded 1-aza-4-benzylbicyclo[3.3.0]oct-4-en-8-one (33).
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Direct radical addition reactions of thiocarbonyl (C=S) groups unaccompanied by β-scission have rarely been reported.
“Direct radical addition reactions of thiocarbonyl (C=S) groups unaccompanied by β-scission have rarely been reported despite their potential for constructing various sulfur-containing compounds.”
From Direct Radical Copolymerizations of Thioamides To Generate Vinyl Polymers with Degradable Thioether Bonds in the Backbones (2023) · cites this paper as [14]
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ChemInform Abstract: Tributylstannane‐Mediated Cyclization of Thionocarboxylic Acid Derivatives.
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- Authors
- Bachi, M. D., Bosch, E., Denenmark, D., & Girsh, D.
- ORCID
- Bosch, Eric
- Venue
- The Journal of Organic Chemistry
- Publisher
- American Chemical Society (ACS)
- Published
- 1992-12
- Volume
- 57
- Issue
- 25
- Pages
- 6803-6810
- ISSN
- 0022-3263 (ISSN-L)
- 1520-6904
- OpenAlex
- W2952239491
- Cited by
- 46
- References
- 0
- Citations by year
- 2025: 1 · 2023: 1 · 2021: 2 · 2020: 1 · 2018: 1 · 2017: 2 · 2015: 1 · 2012: 1
- FWCI
- 2.63
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- The Journal of Organic Chemistry (publishedVersion)
- BearWorks (Missouri State University) (submittedVersion)
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Synthesis and Reactivity of Sulfur-Containing Compounds
- Physical Sciences › Chemistry › Organic Chemistry › Radical Photochemical Reactions
- Physical Sciences › Chemistry › Organic Chemistry › Sulfur-Based Synthesis Techniques
- Keywords
- tributylstannane, thioamides, radical cyclization, intramolecular radical addition, xanthates, homoallylic alcohols, furan formation
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