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N-Substituted carbamoyl radicals are known to exist as mixtures of the respective E- and Z-conformers; see: Sutcliffe, R.; Ingold, K. U. J. Am. Chem. Soc. 1981, 103, 7686. The predominance of rotamers unfavorable to ring formation in secondary carbamoyl radicals is a possible reason for the known reluctance of these radicals to undergo cyclization onto alkenes; see refs 8 and 9a.
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Grainger, R.S.1
Innocenti, P.2
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34
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0346208460
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and ref 9a
-
In principle, a formally 6-endo-cyclized benzylic radical might result from ring expansion of the initial 5-exo ring-closed β-oxoindolinylmethyl radical via 3-exo cyclization onto the adjacent carbonyl group and subsequent β-scission of the ensuing alkoxyl radical; see: Chatgilialoglu, C.; Crich, D.; Komatsu, M.; Ryu, J. Chem. Rev. 1999, 99, 1991 and ref 9a.
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Chatgilialoglu, C.1
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Ryu, J.4
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35
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33645793184
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-
note
-
No evidence for any β-elimination of tosyl radical was gained in previous cyclization reactions of N-tosylcarbamoyl radicals derived from corresponding selenocarbamates, see ref 8.
-
-
-
-
36
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33645768012
-
-
note
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Similar to the analogue 3 (ref 2h), the tosylated tetrahydrothiophene 8 occurred as a mixture of (E)- and (Z)-isomer in unestablished ratio.
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-
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37
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0037414540
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The β-elimination of benzenesulfanyl radical from carbon-centered radicals is faster than that of tosyl radical, see: Timokhin, V. I.; Gastaldi, S.; Bertrand, M. P.; Chatgilialoglu, C. J. Org. Chem. 2003, 68, 3532.
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Bertrand, M.P.3
Chatgilialoglu, C.4
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38
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33645788209
-
-
note
-
A control experiment established that tetrahydrothiophene 3 can be converted to the tosylated analogue 8 upon radical reaction with TsSPh/AIBN in refluxing benzene.
-
-
-
-
39
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-
33645792242
-
-
note
-
A control experiment interestingly showed that the radical chain reaction of S-4-pentynyl benzenecarbothioate with TsSPh/AIBN in refluxing benzene cleanly afforded compound 8 as well as S-phenyl benzenecarbothioate.
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-
-
-
40
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33645767310
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-
note
-
For unclear reasons, the carbamoyl radical 2g could also undergo significant decarbonylation leading to reduced N-(2-isopropenylphenyl)-4- methylbenzenesulfonamide (25%).
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-
-
-
41
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0000654179
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Luo, L.; Bartberger, M. D.; Dolbier, W. R., Jr. J. Am. Chem. Soc. 1997, 119, 12366.
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Luo, L.1
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Dolbier Jr., W.R.3
-
42
-
-
33645772559
-
-
note
-
Comparable yields of pyrrolydinones and indolinones have been reported in previous cyclizations of N-benzylcarbamoyl radicals derived from 1-benzylcarbamoyl-1-methylcyclohexa-2,5-dienes; see ref 9a,b. However, a better yield of pyrrolidinone 4a was achieved when the carbamoyl radical 2a was generated by UV photolysis of the corresponding oxime oxalate amide; see ref 10a.
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-
-
-
43
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12344302496
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DiLabio, G. A.; Scanlan, E. M.; Walton, J. C. Org. Lett. 2005, 7, 155.
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DiLabio, G.A.1
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Walton, J.C.3
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44
-
-
33645783591
-
-
note
-
In principle, pyrrolidinone 4h might also arise from ring enlargement of the initial 4-exo ring-closed β-oxoazetidinylmethyl radical, see ref 12.
-
-
-
-
45
-
-
33645795347
-
-
note
-
Only minor amounts of a mixture of unidentified products were obtained.
-
-
-
-
46
-
-
33645797246
-
-
note
-
13C NMR spectra.
-
-
-
-
47
-
-
33645780070
-
-
note
-
4J of the vinylic proton with the allylic-like ring protons should be larger for the (E)- than for the (Z)-isomer; see ref 2h.
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-
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