Tricyclo[3.2.2.02,4]non-2(4)-ene: synthesis and trapping of a strained cyclopropene

Chenier, Philip J.; Southard, Dale A.

doi:10.1021/jo00301a024

Cited by 16 publications

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“…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%

“…We previously reported on the generation of 8-oxatricyclocyclopropenes 13, 14, and 16 by fluoride-induced elimination, which underwent isomerization to form benzaldehyde (15) and phenyl 4-phenylnaphth-1-yl ketone (17) (Scheme 3). We previously reported on the generation of 8-oxatricyclocyclopropenes 13, 14, and 16 by fluoride-induced elimination, which underwent isomerization to form benzaldehyde (15) and phenyl 4-phenylnaphth-1-yl ketone (17) (Scheme 3).…”

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%

“…Only three 1,3-fused tricycles with a cyclopropene fused to a bicyclic ring skeleton have been reported. We previously reported on the generation of 8-oxatricyclocyclopropenes 13, 14, and 16 by fluoride-induced elimination, which underwent isomerization to form benzaldehyde (15) and phenyl 4-phenylnaphth-1-yl ketone (17) (Scheme 3). [17] We report, herein, a more straightforward method for the generation of tricyclo[3.2.1.0 2,4 ]oct-2(3)-enes and a study of its reactions with water, tetrahydrofuran (THF), and furan.…”

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: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

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

et al. 2012

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“…3,4 Pioneering work in highly strained cyclopropenes with various polycyclic frameworks done by Szeimies has led to some important studies of dehydroquadricyclane (1), 5 tetracyclo[4.1.0.0 2,4 .0 3,5 ]hept-3-ene (2), 6 tricyclo[3.1.0.0 2,6 ]hex-1(6)-ene (3), 6 and tricyclo[4.1.0.0 2,7 ]hept-1(7)-ene (4). 7 There are five 1,2-fused tricyclics with a cyclopropene fused to a bicyclic ring skeleton, tricyclo-[3.2.1.0 2,4 ]oct-2(4)-ene (5), 8 tricyclo[3.2.1.0 2,4 ]octa-2(4),6-diene (6), 9 tricyclo[3.2.2.0 2,4 ]non-2(4)-ene (7), 10 tricyclo-[3.2.2.0 2,4 ]nona-2(4),6-diene (8), 11 and tricyclo[3.3.2.0 2,4 ]dec-2(4)-ene (9), 12 which have been synthesized and trapped. Müller has reported that only reduction of the bromine substituent to the hydrogen occurred and the presumed intermediate organo-Li derivative did not undergo b-elimination reaction when 6,7-benzo-2-bromo-4-chloro-1,5-diphenyl-8oxatricyclo[3.2.1.0 2,4 ]oct-6-ene was reacted with BuLi.…”

Section: Introductionmentioning

confidence: 99%

The Synthesis and Chemistry of 1,3‐Bridged Polycyclic Cyclopropenes: 8‐Oxatricyclo[3.2.1.0^2,4]octa‐2,6‐dienes

Lee

Chang

Cherng

et al. 2004

J Chinese Chemical Soc

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-6,7-benzo-1,5-diphenyl-8-oxatricyclo[3.2.1.0 2,4 ]octa-2,6-diene (12), have been synthesized by elimination of 2-chloro-3-trimethylsilyl-8-oxatricyclo[3.2.1.0 2,4 ]-oct-6-enes, 17, 18 and 30, which were generated from 1-chloro-3-trimethylsilylcyclopropene with furan and diphenylisobenzofuran. We have demonstrated a facile route to synthesize the highly strained 1,3-fused polycyclic cyclopropenes, 10, 11, and 12. The stereochemistry of the Diels-Alder reactions of cyclopropene 16 with furan and DPIBF are different. Cyclopropene 16 was treated with furan to form exo-exo and endo-exo adducts (5:2) and treated with DPIBF to generate an exo-exo adduct. Compounds 10, 11 and 12 undergo isomerization reactions to form benzaldehyde and phenyl 4-phenyl-[1]naphthyl ketone to release strain energies via diradical mechanisms.

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