Isomerization of Tricyclo[3.2.2.0<sup>2,4</sup>]nona-2(4),6-diene to the Anti-Bredt Compound 8-Methylenebicyclo[3.2.1]octa-1,6-diene

Lee, Gon-Ann; Lin, Yu; Huang, Ai Ni; Li, Yi Ching; Jann, Yih-Chyn; Chen, Chi-Sheng

doi:10.1021/ja983199c

Cited by 12 publications

(6 citation statements)

References 29 publications

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“…Decarbonylation followed by β-hydride elimination from 14 or 17 would result in the formation of isobutylene hydride 23 or adamantene hydride complex 35 , respectively. Of particular interest to us was the decarbonylation of 17 , as it presented a possible method for forming metal-stabilized highly strained anti-Bredt bridgehead alkenes. − Unfortunately, we were not able to cleanly promote β-hydride elimination from either 14 or 17 by photoinduced decarbonylation. This lack of clean reactivity provides further support for the tandem nature of the reactions between 1 and aldehydes.…”

Section: Discussionmentioning

confidence: 99%

Alkylation of Iridium via Tandem Carbon−Hydrogen Bond Activation/Decarbonylation of Aldehydes. Access to Complexes with Tertiary and Highly Hindered Metal−Carbon Bonds

2000

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Reactions between Cp*(PMe 3 )Ir(Me)OTf (1) and aldehydes (RCHO) proceed with high selectivity to give the hydrocarbyl carbonyl salts [Cp*(PMe 3 )Ir(R)(CO)][OTf] (R ) Me (2), Et (3), n-Pr (4), c-Pr (5), Ph (6), 1-ethylpropyl (7), p-tolyl (8), mesityl (9), 2-(Z)-1-phenylpropenyl (10), vinyl (13), t-Bu (14), 1-adamantyl ( 17)). This tandem C-H bond activation/decarbonylation reaction provides access to the first isolated tertiary alkyl complexes of iridium. X-ray diffraction studies were performed on mesityl complex 9, tert-butyl derivative 15, and 1-adamantyl compound 18. Decarbonylation of cyclopropyl complex 5 results in irreversible opening of the cyclopropyl ring. This reaction has provided useful information concerning the mechanism of C-H activation of cyclopropane by 1. Hydride reduction of the p-tolyl carbonyl salt 8 has provided an example of a rare transition-metal formyl complex, Cp*-(PMe 3 )Ir(p-tolyl)(CHO) (28).

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Section: Discussionmentioning

confidence: 99%

Alkylation of Iridium via Tandem Carbon−Hydrogen Bond Activation/Decarbonylation of Aldehydes. Access to Complexes with Tertiary and Highly Hindered Metal−Carbon Bonds

2000

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“…gem -Dihalocyclopropanes can be easily transformed into the corresponding halocyclopropenes (for a review, see ref ). Depending on their structure and the method by which they were synthesized, these strained molecules sometimes can be isolated 60,122,389 or trapped by an appropriate reagent, often as their Diels−Alder adducts, ,,,, or can undergo a plethora of further transformations . Many of these reactions are of great importance in organic synthesis.…”

Section: Iv6 Transformations Of Gem-dihalocyclopropanes Into Cyclopro...mentioning

confidence: 99%

Syntheses ofgem-Dihalocyclopropanes and Their Use in Organic Synthesis

2003

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“…11 In order to synthesize this type of 1,3-fused tricyclic cyclopropenes, we generated 1-bromo-2,2-dichloro-3-trimethylsilylcyclopropane (13) as a starting material. 15 Compound 13 (trans:cis = 6:1) was prepared by dichlorocarbene addition to b-bromovinyltrimethylsilane (trans:cis = 12:1).…”

Section: Resultsmentioning

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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Isomerization of Tricyclo[3.2.2.0^2,4]nona-2(4),6-diene to the Anti-Bredt Compound 8-Methylenebicyclo[3.2.1]octa-1,6-diene

Cited by 12 publications

References 29 publications

Alkylation of Iridium via Tandem Carbon−Hydrogen Bond Activation/Decarbonylation of Aldehydes. Access to Complexes with Tertiary and Highly Hindered Metal−Carbon Bonds

Alkylation of Iridium via Tandem Carbon−Hydrogen Bond Activation/Decarbonylation of Aldehydes. Access to Complexes with Tertiary and Highly Hindered Metal−Carbon Bonds

Syntheses ofgem-Dihalocyclopropanes and Their Use in Organic Synthesis

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

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Isomerization of Tricyclo[3.2.2.02,4]nona-2(4),6-diene to the Anti-Bredt Compound 8-Methylenebicyclo[3.2.1]octa-1,6-diene

Cited by 12 publications

References 29 publications

Alkylation of Iridium via Tandem Carbon−Hydrogen Bond Activation/Decarbonylation of Aldehydes. Access to Complexes with Tertiary and Highly Hindered Metal−Carbon Bonds

Alkylation of Iridium via Tandem Carbon−Hydrogen Bond Activation/Decarbonylation of Aldehydes. Access to Complexes with Tertiary and Highly Hindered Metal−Carbon Bonds

Syntheses ofgem-Dihalocyclopropanes and Their Use in Organic Synthesis

The Synthesis and Chemistry of 1,3‐Bridged Polycyclic Cyclopropenes: 8‐Oxatricyclo[3.2.1.02,4]octa‐2,6‐dienes

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Isomerization of Tricyclo[3.2.2.0^2,4]nona-2(4),6-diene to the Anti-Bredt Compound 8-Methylenebicyclo[3.2.1]octa-1,6-diene

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