Cyclopropyl aziridines: solvolytic reactions of the <i>N</i>-tosylaziridines of (+)-2-carene and (+)-3-carene

Silverberg, Lee J.; Rabb, Javon M.; Reno, J. Michael; He, Gang

doi:10.1515/hc-2014-0093

Cited by 4 publications

(3 citation statements)

References 52 publications

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“…It has been demonstrated that the reactivity of the cyclopropyl halonium ions of compound 1 is similar to that of the protonated cyclopropyl epoxide 2 [6] and cyclopropyl tosylaziridine 5 [10]. As expected, the cyclopropyl halonium ions were extremely reactive, but acetonitrile was able to trap them, with 1,4-addition occurring, opening the cyclopropane ring, instead of 1,2-addition occurring, as occurs with halonium ions of compound 3 [27].…”

Section: Resultsmentioning

confidence: 69%

“…We have since found similar behaviour with the tosyl aziridines 5 and 6 (Scheme 3) [8][9][10]. We suggested that in the reactions of compound 2 or 5 with water, the positive charge on the protonated heteroatom was delocalized through the cyclopropane [8][9][10][11][12][13] and both rings were opened in a concerted fashion by the oxygen nucleophile (Scheme 2). This released the strain energy of both rings.…”

Section: Introductionmentioning

confidence: 75%

“…Scheme 2 [6] Scheme 3 [8][9][10] similar products. We anticipated that the tertiary allylic halide might be displaced by another nucleophile (Scheme 4).…”

Section: Scheme 1 [2]mentioning

confidence: 99%

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Reactions of the halonium ions of carenes and pinenes: An experimental and theoretical study

et al. 2015

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The reactions of vinylcyclopropane (+)-2-carene (1) and vinylcyclobutanes (-)-β-pinene (7), (-)-α-pinene (11), and (-)-nopol (12) with electrophilic halogens in the presence of oxygen and nitrogen nucleophiles in various solvents have been investigated. The halonium ion intermediates that were presumably formed were very reactive and led to opening of the conjugated cyclopropane or cyclobutane. Reactions of chloramine-T trihydrate with compound 1 in acetonitrile gave amidine 13 and diazepine 14. Reactions of chloramine-T trihydrate with pinenes in methylene chloride gave allylic tosylamines 22, 16B and 24. Mechanisms to explain the observations are proposed and supported by ab initio and Density Functional Theory calculations on the carenes and pinenes in this report and their bromonium ion intermediates. For comparisons, the relative extent of conjugation with the bromonium ion moiety of these, as well as select cyclohexene and cyclohexadiene systems and their corresponding bromonium ions, were optimized at the B3LYP/cc-pVDZ level of theory, and then these geometries were analyzed using the absolute hardness index at the HartreeFock/aug-cc-pVDZ and B3LYP/aug-cc-pVDZ levels of theory. Additionally, Natural Population Analysis charges were calculated for these systems using Møller-Plessett Second-Order Perturbation Theory electron densities and the aug-cc-pVDZ basis set. Combining the results of these theoretical methods with analysis of structural details of their optimized geometries gives much electronic structure insight into the extent of conjugation of bromonium ions of the carenes and pinenes reported here, and places them in relative context of more traditional conjugated and non-conjugated bromonium ion systems. In particular, bromonium ions of compounds 1, 7, and 11 display structural distortions, charge delocalizations and hardness values comparable with those of traditional conjugated cyclohexadienes, with possible reasons for subtle differences presented.

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Section: Resultsmentioning

confidence: 69%

Section: Introductionmentioning

confidence: 75%

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Reactions of the halonium ions of carenes and pinenes: An experimental and theoretical study

et al. 2015

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Stereoselective Synthesis of Contiguous Cyclopropylaziridines: Enabling the Construction of Versatile Chiral Molecules Including γ‐Lactams via Ring‐Opening Reactions

Han

Yang

2023

Adv Synth Catal

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The synthesis of chiral contiguous cyclopropylaziridine was achieved through cyclopropanation of (E)‐3‐((S)‐1‐[(R)‐1‐phenylethyl)aziridin‐2‐yl]acrylaldehyde with bromomalonate in the presence of (2R)‐ or (2S)‐[diphenyl(trimethylsilyloxy) methyl]pyrrolidine as a chiral organocatalyst and 2,6‐lutidine as a base. This chiral cyclopropylaziridine was then subjected to various functional transformations, leading to the construction of a wide range of structurally important motifs.

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Synthesis of new chiral arylsulfonamides based on carane amino alcohols

Grebyonkina,

Banina,

Rumyantsev

et al. 2024

Russ Chem Bull

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Cyclopropyl aziridines: solvolytic reactions of the N-tosylaziridines of (+)-2-carene and (+)-3-carene

Cited by 4 publications

References 52 publications

Reactions of the halonium ions of carenes and pinenes: An experimental and theoretical study

Reactions of the halonium ions of carenes and pinenes: An experimental and theoretical study

Stereoselective Synthesis of Contiguous Cyclopropylaziridines: Enabling the Construction of Versatile Chiral Molecules Including γ‐Lactams via Ring‐Opening Reactions

Synthesis of new chiral arylsulfonamides based on carane amino alcohols

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