Synthesis and chemistry of some tricyclic cyclopropenes. 3. Tricyclo[3.2.1.02,4]oct-2(4)-ene

Chenier, Philip J.; Bauer, Michael J.; Hodge, Christina L.

doi:10.1021/jo00048a032

Cited by 24 publications

(13 citation statements)

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“…13 C NMR spectra were measured in CDCl 3 or [D 6 ]acetone solution with a 75 MHz NMR spectrometer and referenced to CDCl 3 (δ = 77.0 ppm) or [D 6 ]acetone (δ = 29.8 ppm). 1 H NMR spectra were recorded in CDCl 3 solution with a 300 MHz NMR spectrometer by using the signal of residual solvent protons (δ = 7.26 ppm) as internal standard.…”

Section: Methodsmentioning

confidence: 99%

“…1 H NMR spectra were recorded in CDCl 3 solution with a 300 MHz NMR spectrometer by using the signal of residual solvent protons (δ = 7.26 ppm) as internal standard. 13 Chemical shifts (δ) are expressed in ppm downfield from tetramethylsilane.…”

Section: Methodsmentioning

confidence: 99%

“…1 H NMR spectra were recorded in CDCl 3 solution with a 300 MHz NMR spectrometer by using the signal of residual solvent protons (δ = 7.26 ppm) as internal standard. 13 C NMR spectra were measured in CDCl 3 or [D 6 ]acetone solution with a 75 MHz NMR spectrometer and referenced to CDCl 3 (δ = 77.0 ppm) or [D 6 ]acetone (δ = 29.8 ppm). Chemical shifts (δ) are expressed in ppm downfield from tetramethylsilane.…”

Section: Methodsmentioning

confidence: 99%

“…1 kcal/mol. [12g] There are four 1,2-fused tricycles with a cyclopropene fused to a bicyclic ring skeleton, tricyclo[3.2.1.0 2,4 ]oct-2(4)-ene (9), [13] tricyclo[3.2.1.0 2,4 ]octa-2(4),6-diene (10), [14] tricyclo-[3.2.2.0 2,4 ]non-2(4)-ene (11), [15] and tricyclo[3.2.2.0 2,4 ]nona-2(4),6-diene (12), [16] all of which have been generated and trapped (Scheme 2). Formation of vinylcarbene 2 and conversion into 3 reported by Zuev and Sheridan.…”

Section: Introductionmentioning

confidence: 99%

“…[11] Pioneering work in highly strained cyclopropenes with various polycyclic frameworks performed by Szeimies has led to some important studies of dehydroquadricyclane (4), [12a-12c] tetracyclo[4.1.0.0 2,4 .0 3,5 ]hept-3-ene (5), [12d] tricyclo[3.1.0.0 2,6 ]hex-1(6)-ene (6), [12d] and tricyclo[4.1.0.0 2,7 ]hept-1(7)-ene (7), [12e,12f] and de Meijere et al have also generated bicyclo[2.1.0]pent-1(4)-ene derivative 8. [12g] There are four 1,2-fused tricycles with a cyclopropene fused to a bicyclic ring skeleton, tricyclo[3.2.1.0 2,4 ]oct-2(4)-ene (9), [13] tricyclo[3.2.1.0 2,4 ]octa-2(4),6-diene (10), [14] tricyclo-[3.2.2.0 2,4 ]non-2(4)-ene (11), [15] and tricyclo[3.2.2.0 2,4 ]nona-2(4),6-diene (12), [16] all of which have been generated and trapped (Scheme 2). Scheme 2.…”

Section: Introductionmentioning

confidence: 99%

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Generation and Chemistry of Tricyclo[3.2.1.0^2,4]oct‐2(3)‐ene

et al. 2012

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The 1,3‐fused polycyclic cyclopropene, tricyclo[3.2.1.02,4]oct‐2(3)‐ene 25, was synthesized by the elimination of trimethylsilyl chloride from 2‐chloro‐3‐(trimethylsilyl)tricyclo[3.2.1.02,4]octane 20. However, the high strain in the system favors the ring‐opened vinylcarbene form, which undergoes a number of reactions including the addition of water, insertion into the C–H bond α to the oxygen atom in tetrahydrofuran (THF), and [1+2] addition to the C=C bond in furan. The stereoselectivity of the addition of H2O and THF to the vinylcarbene are similar, and exo products were preferably formed. As a result of electronic and steric effects, intermediate 26 reacted with furan and preferentially yielded the endo product 27. Furthermore, on heating, the addition products 27 and 28 rearranged to aldehyde 29.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%