Details
| Original language | English |
|---|---|
| Pages (from-to) | 4363-4372 |
| Number of pages | 10 |
| Journal | European Journal of Organic Chemistry |
| Issue number | 22 |
| Publication status | Published - 3 Nov 2003 |
Abstract
The reaction between rac-(benzocyclobutenone)tricarbonylchromium (rac-1) and lithium diisopropylphosphide (LDP) or lithium di-tert-butylphosphide, unlike its reaction with lithium diisopropylamide (LDA), results in a distal ring-opening, with formation of acylphosphane derivatives. The tricarbonylchromium complex rac-6 of 2-methylbenzoyldiisopropylphosphane has been structurally characterized. The reaction proceeds through the corresponding benzylic anion intermediate, which was shown to react with ketones or aldehydes with formation of isochromanone derivatives. This indicates that a dialkylphosphide is a much better leaving group than an amide. The availability of 1 in enantiomerically pure form inspired an inspection of the diastereoselectivity of the cyclization with aldehydes. It was found that the reaction between the intermediate and benzaldehyde took place with complete diastereoselectivity, thus establishing a route to enantiomerically pure 3-phenyhsochromanone.
Keywords
- Arene ligands, Chromium, Isochromanone, Lithium dialkylphosphides, Spiro compounds
ASJC Scopus subject areas
- Chemistry(all)
- Physical and Theoretical Chemistry
- Chemistry(all)
- Organic Chemistry
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In: European Journal of Organic Chemistry, No. 22, 03.11.2003, p. 4363-4372.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Reactions between Benzocyclobutenone Tricarbonylchromium Complexes and Lithium Dialkylphosphides
T2 - A New Route to Isochromanones
AU - Schnebel, Matthias
AU - Weidner, Ingo
AU - Wartchow, Rudolf
AU - Butenschön, Holger
PY - 2003/11/3
Y1 - 2003/11/3
N2 - The reaction between rac-(benzocyclobutenone)tricarbonylchromium (rac-1) and lithium diisopropylphosphide (LDP) or lithium di-tert-butylphosphide, unlike its reaction with lithium diisopropylamide (LDA), results in a distal ring-opening, with formation of acylphosphane derivatives. The tricarbonylchromium complex rac-6 of 2-methylbenzoyldiisopropylphosphane has been structurally characterized. The reaction proceeds through the corresponding benzylic anion intermediate, which was shown to react with ketones or aldehydes with formation of isochromanone derivatives. This indicates that a dialkylphosphide is a much better leaving group than an amide. The availability of 1 in enantiomerically pure form inspired an inspection of the diastereoselectivity of the cyclization with aldehydes. It was found that the reaction between the intermediate and benzaldehyde took place with complete diastereoselectivity, thus establishing a route to enantiomerically pure 3-phenyhsochromanone.
AB - The reaction between rac-(benzocyclobutenone)tricarbonylchromium (rac-1) and lithium diisopropylphosphide (LDP) or lithium di-tert-butylphosphide, unlike its reaction with lithium diisopropylamide (LDA), results in a distal ring-opening, with formation of acylphosphane derivatives. The tricarbonylchromium complex rac-6 of 2-methylbenzoyldiisopropylphosphane has been structurally characterized. The reaction proceeds through the corresponding benzylic anion intermediate, which was shown to react with ketones or aldehydes with formation of isochromanone derivatives. This indicates that a dialkylphosphide is a much better leaving group than an amide. The availability of 1 in enantiomerically pure form inspired an inspection of the diastereoselectivity of the cyclization with aldehydes. It was found that the reaction between the intermediate and benzaldehyde took place with complete diastereoselectivity, thus establishing a route to enantiomerically pure 3-phenyhsochromanone.
KW - Arene ligands
KW - Chromium
KW - Isochromanone
KW - Lithium dialkylphosphides
KW - Spiro compounds
UR - http://www.scopus.com/inward/record.url?scp=0345276419&partnerID=8YFLogxK
U2 - 10.1002/ejoc.200300390
DO - 10.1002/ejoc.200300390
M3 - Article
AN - SCOPUS:0345276419
SP - 4363
EP - 4372
JO - European Journal of Organic Chemistry
JF - European Journal of Organic Chemistry
SN - 1434-193X
IS - 22
ER -