Issue 3, 2000

The cyclization of N-butylpent-4-enylaminyl revisited: a combined theoretical and experimental study

Abstract

The cyclization reactions of N-methylpent-4-enylaminyl (10), hex-5-enyl (11) and pent-4-en-1-oxyl (12) radicals were investigated theoretically at the CBS-RAD(B3LYP, B3LYP) level of theory. In all three cases the correspondence between calculated and experimental data was excellent. N-Methylpent-4-enylaminyl (10) is predicted to undergo irreversible (ΔG = −5.4 kcal mol−1; ΔG = 12.1 kcal mol−1) cyclization through the 5-exo manifold. The role of (Bu3Sn)2O in the reactions of arenesulfenamides 6–9 and N-butyl-2-[(phenylselenyl)methyl]pyrrolidine (15) with Bu3SnH in benzene at 80 °C has been reassessed. The purpose of (Bu3Sn)2O in these reactions is to scavenge 2-mercaptobenzothiazole and PhSeH, respectively, which are produced in situ from the reaction of adventitious bis(benzothiazol-2-yl) disulfide and PhSeSePh, respectively, and Bu3SnH. The reaction of N-butyl-2-[(phenylselenyl)methyl]pyrrolidine (15) with Bu3SnH was reinvestigated and found to produce only N-butyl-2-methylpyrrolidine (16) thus confirming the irreversible nature of the cyclization of N-methylpent-4-enylaminyl (10) under the conditions employed in this study.

Supplementary files

Additions and corrections

Article information

Article type
Paper
Submitted
10 Dec 1999
Accepted
21 Dec 1999
First published
15 Feb 2000

J. Chem. Soc., Perkin Trans. 2, 2000, 425-431

The cyclization of N-butylpent-4-enylaminyl revisited: a combined theoretical and experimental study

B. J. Maxwell, B. J. Smith and J. Tsanaktsidis, J. Chem. Soc., Perkin Trans. 2, 2000, 425 DOI: 10.1039/A909747C

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