Formal synthesis of erythrodiene and spirojatamol via rhodium-catalysed claisen rearrangement/hydroacylation

Tetrahedron Letters

Volumn 39, Issue 52, 1998, Pages 9647-9648

  Sattelkau, Tim ^a   Eilbracht, Peter ^a  

^a TU DORTMUND UNIVERSITY   (Germany)

Author keywords

Catalysis; Natural Products; Spiro Compounds

Indexed keywords

ERYTHRODIENE; NATURAL PRODUCT; RHODIUM COMPLEX; SPIRO COMPOUND; SPIROJATAMOL; UNCLASSIFIED DRUG;

ACYLATION; ARTICLE; CATALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; CYCLIZATION; DIASTEREOISOMER; DRUG SYNTHESIS; ENANTIOMER;

EID: 0032564617     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(98)02325-9     Document Type: Article

References (20)

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12. [6] 5.00g (24mmol) 2-allyloxymethylene-4-isopropyl-cyclohexanone (3) are heated in 3.0g tetradecane for 8h at 174°C. The reaction mixture is chromatographed on silica gel (hexanes/MTBE), yielding 0.34g (2mmol, 8%) cis-2-allyl-4-isopropyl-cyclohexanone (6), 1.85g (9mmol, 37%) (1S*,5R*)-1-allyl-2-oxo-5-isopropyl-cyclohexanecarbaldehyde (2) and 2.22g (10mmol, 44%) (1R*,5R*)-2. Relative stereochemistry was established by NOESY spectroscopy and confirmed by the known products 1 from the next reaction step.
13. 3
14. [8] The use of [Rh(dppe)(nbd)]ClO4 as a catalyst precursor, an effective system reported to yield only minimum or no decarbonylation products, here leads to quantitative decarbonylation of 2. See D.P. Fairlie, B. Bosnich, Organometallics 1988, 7, 936-945.
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20. [12] 6 is accompanied by various isomers resulting from double-bond migration.