Journal
JOURNAL OF ORGANIC CHEMISTRY
Volume 79, Issue 12, Pages 5717-5727Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jo5008509
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- Japan Society for the Promotion of Sciences [25460154, 25860091]
- Grants-in-Aid for Scientific Research [25860091, 25460154] Funding Source: KAKEN
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The atropisomeric and conformational properties of 1,5-benzodiazepines with an N-sulfonyl (p-tosyl/mesyl) group (IIa/b) were investigated by comparison with those of the N-benzoyl congeners (I). Similar to I, when the Ar-N(SO2) axis was frozen by a C9-substitution in the molecules, IIa/b were separated into the (aR)- and (aS)-atropisomers. The conformation of Ila/b revealed that the substituent (p-tolyl/methyl group) in the sulfonyl moiety occupies the position over the diazepine ring (folded form) in both the solid and solution states [e.g., (+)-(aR)-N-p-tosyl-1,5-benzodiazepin-2-one (IIa-2)], whereas that of I is anti to the diazepine ring [e.g., (-)-(aR)-N-benzoyl-1,5-benzodiazepin-2-one (I-2)], which was further supported by a computational study. The stereochemical stability also differed between the two congeners (e.g., Delta G double dagger: 104 kJ/mol for 1-2, and 132 kJ/mol for IIa-2).
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