Carbocyclic cis-[1.1.1]-tris-σ-homobenzenes - Syntheses by triple epoxide → cyclopropane conversions, structural data, [σ2s+σ2s+σ2s] cycloreversions

Publikation: Beiträge in ZeitschriftenZeitschriftenaufsätzeForschungbegutachtet

Standard

Carbocyclic cis-[1.1.1]-tris-σ-homobenzenes - Syntheses by triple epoxide → cyclopropane conversions, structural data, [σ2s+σ2s+σ2s] cycloreversions. / Rücker, Christoph; Müller-Bötticher, Hermann; Braschwitz, Wolf-Dieter et al.
in: Liebigs Annalen - recueil, Jahrgang 1997, Nr. 5, 01.05.1997, S. 967-989.

Publikation: Beiträge in ZeitschriftenZeitschriftenaufsätzeForschungbegutachtet

Harvard

APA

Vancouver

Rücker C, Müller-Bötticher H, Braschwitz WD, Prinzbach H, Reifenstahl U, Irngartinger H. Carbocyclic cis-[1.1.1]-tris-σ-homobenzenes - Syntheses by triple epoxide → cyclopropane conversions, structural data, [σ2s+σ2s+σ2s] cycloreversions. Liebigs Annalen - recueil. 1997 Mai 1;1997(5):967-989. doi: 10.1002/jlac.199719970528

Bibtex

@article{f2dfcc20662c4b4dba73c5eca0463010,
title = "Carbocyclic cis-[1.1.1]-tris-σ-homobenzenes - Syntheses by triple epoxide → cyclopropane conversions, structural data, [σ2s+σ2s+σ2s] cycloreversions",
abstract = "By triple epoxide → cyclopropane transformation starting from cis-benzene trioxide the 3α,6α,9α-tris(TIPS-ethynyl) (1b), -tris(alkoxycarbonyl) (1d, e), -tricyano (1f), and -tris(ammoniomethyl) (1j) derivatives of the still elusive parent cis-[1.1.1]-tris-σ-homobenzene (1a) have been synthesized. Out of a number of carbon nucleophiles tested, a weakly basic mixed cyanocuprate of Li-TIPS-propyne proved the reagent of choice: Eliminations were largely avoided, the scyllo [*]-2,4,6-tris(TIPS-propargyl)cyclohexane-1,3,5-triol (13a), obtained in a stereoselective one-pot threefold epoxide opening (up to 69%), allowed the pertinent functional group manipulations. The selectivity of the base-induced triple cyclopropane ring closure in the flexible cyclohexane precursors strongly depends on the activating groups and is promoted by fixation of the {"}all-axial{"} conformation as an adamantoid orthophosphate. The ΔG ≠ values determined for the generally neat 3σ → 3π isomerizations [28.5 (1e), 29.0 (1f), 22.6 (1j) kcal mol -1] are in line with concerted reaction courses ([σ2s+σ2s+σ2s]). For the trinitrile 1f an X-ray structure analysis confirmed a nearly planar cyclohexane ring and a relatively large cyclohexane/cyclopropane interplanary angle (113°).",
keywords = "Chemistry, cis-[1.1.1]-Tris-σ-homobenzenes, Substituent effects, [σ2s+σ2s+σ2s] Cycloreversions",
author = "Christoph R{\"u}cker and Hermann M{\"u}ller-B{\"o}tticher and Wolf-Dieter Braschwitz and Horst Prinzbach and Uwe Reifenstahl and Hermann Irngartinger",
year = "1997",
month = may,
day = "1",
doi = "10.1002/jlac.199719970528",
language = "English",
volume = "1997",
pages = "967--989",
journal = "Liebigs Annalen - recueil",
issn = "0947-3440",
publisher = "Wiley-VCH Verlag",
number = "5",

}

RIS

TY - JOUR

T1 - Carbocyclic cis-[1.1.1]-tris-σ-homobenzenes - Syntheses by triple epoxide → cyclopropane conversions, structural data, [σ2s+σ2s+σ2s] cycloreversions

AU - Rücker, Christoph

AU - Müller-Bötticher, Hermann

AU - Braschwitz, Wolf-Dieter

AU - Prinzbach, Horst

AU - Reifenstahl, Uwe

AU - Irngartinger, Hermann

PY - 1997/5/1

Y1 - 1997/5/1

N2 - By triple epoxide → cyclopropane transformation starting from cis-benzene trioxide the 3α,6α,9α-tris(TIPS-ethynyl) (1b), -tris(alkoxycarbonyl) (1d, e), -tricyano (1f), and -tris(ammoniomethyl) (1j) derivatives of the still elusive parent cis-[1.1.1]-tris-σ-homobenzene (1a) have been synthesized. Out of a number of carbon nucleophiles tested, a weakly basic mixed cyanocuprate of Li-TIPS-propyne proved the reagent of choice: Eliminations were largely avoided, the scyllo [*]-2,4,6-tris(TIPS-propargyl)cyclohexane-1,3,5-triol (13a), obtained in a stereoselective one-pot threefold epoxide opening (up to 69%), allowed the pertinent functional group manipulations. The selectivity of the base-induced triple cyclopropane ring closure in the flexible cyclohexane precursors strongly depends on the activating groups and is promoted by fixation of the "all-axial" conformation as an adamantoid orthophosphate. The ΔG ≠ values determined for the generally neat 3σ → 3π isomerizations [28.5 (1e), 29.0 (1f), 22.6 (1j) kcal mol -1] are in line with concerted reaction courses ([σ2s+σ2s+σ2s]). For the trinitrile 1f an X-ray structure analysis confirmed a nearly planar cyclohexane ring and a relatively large cyclohexane/cyclopropane interplanary angle (113°).

AB - By triple epoxide → cyclopropane transformation starting from cis-benzene trioxide the 3α,6α,9α-tris(TIPS-ethynyl) (1b), -tris(alkoxycarbonyl) (1d, e), -tricyano (1f), and -tris(ammoniomethyl) (1j) derivatives of the still elusive parent cis-[1.1.1]-tris-σ-homobenzene (1a) have been synthesized. Out of a number of carbon nucleophiles tested, a weakly basic mixed cyanocuprate of Li-TIPS-propyne proved the reagent of choice: Eliminations were largely avoided, the scyllo [*]-2,4,6-tris(TIPS-propargyl)cyclohexane-1,3,5-triol (13a), obtained in a stereoselective one-pot threefold epoxide opening (up to 69%), allowed the pertinent functional group manipulations. The selectivity of the base-induced triple cyclopropane ring closure in the flexible cyclohexane precursors strongly depends on the activating groups and is promoted by fixation of the "all-axial" conformation as an adamantoid orthophosphate. The ΔG ≠ values determined for the generally neat 3σ → 3π isomerizations [28.5 (1e), 29.0 (1f), 22.6 (1j) kcal mol -1] are in line with concerted reaction courses ([σ2s+σ2s+σ2s]). For the trinitrile 1f an X-ray structure analysis confirmed a nearly planar cyclohexane ring and a relatively large cyclohexane/cyclopropane interplanary angle (113°).

KW - Chemistry

KW - cis-[1.1.1]-Tris-σ-homobenzenes

KW - Substituent effects

KW - [σ2s+σ2s+σ2s] Cycloreversions

UR - http://www.scopus.com/inward/record.url?scp=0345970701&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/62c3684d-30b2-34a8-a4a9-30ffb3d7f993/

U2 - 10.1002/jlac.199719970528

DO - 10.1002/jlac.199719970528

M3 - Journal articles

VL - 1997

SP - 967

EP - 989

JO - Liebigs Annalen - recueil

JF - Liebigs Annalen - recueil

SN - 0947-3440

IS - 5

ER -

DOI

Zuletzt angesehen

Publikationen

  1. Stereotyp
  2. On entrepreneurial risk-taking and the macroeconomic effects of financial constraints
  3. Re-registration as a means of altering a company's status
  4. Healthy Eating and Physical Activity in Schools
  5. Lost in the Rhythm
  6. Machine learning for optimization of energy and plastic consumption in the production of thermoplastic parts in SME
  7. Die Polizei in gewaltsamen Protestdynamiken
  8. Tristan Garcia, Form and Object
  9. INSA Indicator System Sustainable Agriculture
  10. Extended Income Dynamics
  11. Entwicklung und realisierung eines computer-basierten lernprogramms zur GMP-schulung/Programm-entwicklung und benutzer-akzeptanz
  12. Egozentrierte Netzwerkanalysen
  13. VIPs in der Lesesozialisation ?
  14. Multimodality
  15. Don't be upset! Can cars regulate anger by communication?
  16. Effects of introspective vs. extraspective instruction in scaling of hedonic properties of flavouring ingredients by Chinese and German subjects
  17. Art Work as Life Work
  18. Human development and the "explosion" of democracy
  19. Factors affecting fruit set in Aizoaceae species of the Succulent Karoo
  20. Contrasting changes in the abundance and diversity of North American bird assemblages from 1971 to 2010
  21. Sensory Engineering
  22. You Can't Always Get What You Want
  23. Monitoring the Monitor? Selective Responses to Human Rights Transgressions
  24. Performance decline in low-stakes educational assessments
  25. High temperature deformation of magnesium alloy TX32-0.4Al-0.8Si
  26. Cinephilia in transition
  27. Zootechnologien
  28. Tri‐trophic interaction networks along a tree diversity gradient of BEF‐China
  29. Cognitive load theory
  30. Predicting the interfacial heat transfer coefficient of cast Mg-Al alloys using Beck's inverse analysis
  31. Symmetry-aided computation of the detour matrix and the detour index
  32. Ergebnisse einer Sparkassen-Umfrage
  33. Secondary School Students’ Perceptions of Autonomy, Competence, and Relatedness in Digital Learning
  34. Artificial intelligence in sustainable development research
  35. Learning Soccer in Elementary School: Using Teaching Games for Understanding and Digital Media
  36. Piloting Citizen Science Methods to Measure Perceptions of Carbon Footprint and Energy Content of Food
  37. Ein gemeinsamer europäischer Referenzrahmen für Sprachen oder für Englisch?
  38. Reinventing the Politics of Knowledge Production in Migration Studies
  39. Policy schemes, operational strategies and system integration of residential co-generation fuel cells.
  40. Back for more
  41. Influence of Torsion on Precipitation and Hardening Effects during Aging of an Extruded AZ91 Alloy
  42. Hermann Bahr