Details
| Original language | English |
|---|---|
| Pages (from-to) | 57-62 |
| Number of pages | 6 |
| Journal | Pure and Applied Chemistry |
| Volume | 74 |
| Issue number | 1 |
| Publication status | Published - 14 Jul 2002 |
| Event | 11th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS-11) - Taipei, Taiwan Duration: 22 Jul 2001 → 26 Jul 2001 http://publications.iupac.org/pac/2002/pdf/7401x0057.pdf |
Abstract
Tricarbonylchromium complexes of benzocyclobutenone, benzocyclobutenedione, and 1,3-indandione are readily prepared by hydrolysis of the complexes of the corresponding acetals. Reduction of the benzocyclobutenone complex gives rise to an oxy-anion-driven ring opening to the corresponding ortho-quinodimethane intermediate, which can be trapped with dienophiles. Addition of 1-ethoxy-1-lithioethene allows a stereoselective ring expansion followed by an anionic ketol rearrangement with complete diastereoselectivity. Addition of 1-lithio-1-methoxyallene gives rise to a rare anionic 1-vinylcyclobutenol-cyclohexadienol rearrangement. Diaddition of alkenylmetal reagents at both keto groups in benzoyclobutenedione complexes causes dianionic oxy-Cope rearrangements to occur at -78°C, which are followed by diastereoselective intramolecular aldol additions. In some cases, a completely regioselective mono hydrolysis of di(enolates) was observed. Dianionic oxy-Cope rearrangements can also be realized with unstrained benzil derivatives giving 1,6-hexanediones and the corresponding aldol adducts. The 1,2,3-indantrione complex is obtained by oxidation of the 1,3-indandione complex with dimethyldioxirane in good yield and reacts with its central ketone group in hetero Diels-Alder cycloadditions.
ASJC Scopus subject areas
- Chemistry(all)
- General Chemistry
- Chemical Engineering(all)
- General Chemical Engineering
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In: Pure and Applied Chemistry, Vol. 74, No. 1, 14.07.2002, p. 57-62.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Arene chromium complexes with functionalized anellated rings. Selective formation of highly substituted polycycles
AU - Butenschön, Holger
N1 - Funding information: This work was kindly supported by the VolkswagenStiftung, the Deutsche Forschungsgemeinschaft, the Gottlieb Daimler-und Carl Benz-Stiftung, the Fonds der Chemischen Industrie, and the Innovationsoffensive “Biologisch aktive Naturstoffe: Synthetische Diversität”.
PY - 2002/7/14
Y1 - 2002/7/14
N2 - Tricarbonylchromium complexes of benzocyclobutenone, benzocyclobutenedione, and 1,3-indandione are readily prepared by hydrolysis of the complexes of the corresponding acetals. Reduction of the benzocyclobutenone complex gives rise to an oxy-anion-driven ring opening to the corresponding ortho-quinodimethane intermediate, which can be trapped with dienophiles. Addition of 1-ethoxy-1-lithioethene allows a stereoselective ring expansion followed by an anionic ketol rearrangement with complete diastereoselectivity. Addition of 1-lithio-1-methoxyallene gives rise to a rare anionic 1-vinylcyclobutenol-cyclohexadienol rearrangement. Diaddition of alkenylmetal reagents at both keto groups in benzoyclobutenedione complexes causes dianionic oxy-Cope rearrangements to occur at -78°C, which are followed by diastereoselective intramolecular aldol additions. In some cases, a completely regioselective mono hydrolysis of di(enolates) was observed. Dianionic oxy-Cope rearrangements can also be realized with unstrained benzil derivatives giving 1,6-hexanediones and the corresponding aldol adducts. The 1,2,3-indantrione complex is obtained by oxidation of the 1,3-indandione complex with dimethyldioxirane in good yield and reacts with its central ketone group in hetero Diels-Alder cycloadditions.
AB - Tricarbonylchromium complexes of benzocyclobutenone, benzocyclobutenedione, and 1,3-indandione are readily prepared by hydrolysis of the complexes of the corresponding acetals. Reduction of the benzocyclobutenone complex gives rise to an oxy-anion-driven ring opening to the corresponding ortho-quinodimethane intermediate, which can be trapped with dienophiles. Addition of 1-ethoxy-1-lithioethene allows a stereoselective ring expansion followed by an anionic ketol rearrangement with complete diastereoselectivity. Addition of 1-lithio-1-methoxyallene gives rise to a rare anionic 1-vinylcyclobutenol-cyclohexadienol rearrangement. Diaddition of alkenylmetal reagents at both keto groups in benzoyclobutenedione complexes causes dianionic oxy-Cope rearrangements to occur at -78°C, which are followed by diastereoselective intramolecular aldol additions. In some cases, a completely regioselective mono hydrolysis of di(enolates) was observed. Dianionic oxy-Cope rearrangements can also be realized with unstrained benzil derivatives giving 1,6-hexanediones and the corresponding aldol adducts. The 1,2,3-indantrione complex is obtained by oxidation of the 1,3-indandione complex with dimethyldioxirane in good yield and reacts with its central ketone group in hetero Diels-Alder cycloadditions.
UR - http://www.scopus.com/inward/record.url?scp=0036291483&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:0036291483
VL - 74
SP - 57
EP - 62
JO - Pure and Applied Chemistry
JF - Pure and Applied Chemistry
SN - 0033-4545
IS - 1
T2 - 11th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS-11)
Y2 - 22 July 2001 through 26 July 2001
ER -