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Journal article
Sequential Diels-Alder/[3,3]- sigmatropic rearrangement reactions of beta-nitrostyrene with 3-methyl-1,3-pentadiene
Beilstein journal of organic chemistry, v 9(1), pp 2137-2146
17 Oct 2013
PMID: 24204426
Featured in Collection : UN Sustainable Development Goals @ Drexel
Abstract
The tin(IV)-catalyzed reaction of beta-nitrostyrene with (E)-3-methyl-1,3-pentadiene in toluene afforded two major nitronic ester cycloadducts in 27% and 29% yield that arise from the reaction at the less substituted diene double bond. Also present were four cycloadducts from the reaction at the higher substituted diene double bond, two of which were the formal cycloadducts of (Z)-3methyl- 1,3-pentadiene. A Friedel-Crafts alkylation product from the reaction of the diene, beta-nitrostyrene, and toluene was also obtained in 10% yield. The tin(IV)-catalyzed reaction of beta-nitrostyrene with (Z)-3-methyl-1,3-pentadiene in dichloromethane afforded four nitronic ester cycloadducts all derived from the reaction at the higher substituted double bond. One cycloadduct was isolated in 45% yield and two others are formal adducts of the E-isomer of the diene. The product formation in these reactions is consistent with a stepwise mechanism involving a zwitterionic intermediate. The initially isolated nitronic ester cycloadducts underwent tin(IV)-catalyzed interconversion, presumably via zwitterion intermediates. Cycloadducts derived from the reaction at the less substituted double bond of (E)-3-methyl-1,3-pentadiene underwent a [3,3]-sigmatropic rearrangement on heating to afford 4-nitrocyclohexenes. Cycloadducts derived from the reaction at the higher substituted diene double bond of either diene failed to undergo a thermal rearrangement. Rates and success of the rearrangement are consistent with a concerted mechanism possessing a dipolar transition state. An initial assessment of substituent effects on the rearrangement process is presented.
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Details
- Title
- Sequential Diels-Alder/[3,3]- sigmatropic rearrangement reactions of beta-nitrostyrene with 3-methyl-1,3-pentadiene
- Creators
- Peter A. Wade - Drexel UniversityAlma Pipic - Drexel Univ, Dept Chem, Philadelphia, PA 19104 USAMatthias Zeller - Youngstown State Univ, Dept Chem, Youngstown, OH 44555 USAPanagiota Tsetsakos - Drexel Univ, Dept Chem, Philadelphia, PA 19104 USA
- Publication Details
- Beilstein journal of organic chemistry, v 9(1), pp 2137-2146
- Publisher
- Beilstein-Institut
- Number of pages
- 10
- Grant note
- Youngstown State University CAP-491 / Ohio Board of Regents Grant 0087210, / NSF; National Science Foundation (NSF)
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- [Retired Faculty]
- Web of Science ID
- WOS:000325855800002
- Scopus ID
- 2-s2.0-84886803307
- Other Identifier
- 991019167913504721
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- Collaboration types
- Domestic collaboration
- Web of Science research areas
- Chemistry, Organic