Progress toward the total synthesis of bacchopetiolone: Application of a tandem aromatic oxidation/Diels-Alder reaction

Organic Letters

Volumn 8, Issue 24, 2006, Pages 5421-5424

  Bérubé, Amélie ^a   Drutu, Ioana ^a   Wood, John L ^a,b  

^a YALE UNIVERSITY   (United States)

^b Department of Environmental and Radiological Health Sciences   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BACCHOPETIOLONE; DYES, REAGENTS, INDICATORS, MARKERS AND BUFFERS; SESQUITERPENE; UNCLASSIFIED DRUG;

ARTICLE; HYDROLYSIS; OXIDATION REDUCTION REACTION; STEREOISOMERISM; SYNTHESIS; X RAY CRYSTALLOGRAPHY;

CRYSTALLOGRAPHY, X-RAY; HYDROLYSIS; INDICATORS AND REAGENTS; OXIDATION-REDUCTION; SESQUITERPENES; STEREOISOMERISM;

EID: 33846007263     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol061737h     Document Type: Article

References (12)

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6. It is important to note that this homochiral dimerization involves two stereoselective steps, lactone formation and a Diels-Alder reaction. On the basis of simple ground-state energy calculations (e.g., MM2 and MNDO), the product selectivity observed in each step cannot be attributed solely to product stability. The energetic features underpinning what appear to be kinetic selectivities have yet to be fully delineated and require investigation beyond the scope of the current manuscript.
7. The yield of this reaction is based on isolation of a mixture of mono-opened lactones and resubjecting them to the reaction conditions to isolate 15 in 86% combined yield.
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9. Completion of the synthesis from intermediate 21 would require hydrolysis of the urethane followed by deamination. For leading references regarding the latter, see: Barton, D. H. R.; Bringmann, G.; Lamotte, G.; Motherwell, R. S. H.; Motherwell, W. B. Tetrahedron Lett. 1979, 2291.
10. Bravais lattice and space group assignments were unambiguous. Solution and refinement in the space group P-1 yielded promising initial results; however subsequent refinements were ineffective, and geometric parameters deviated significantly from the expected values. The light atom structure possessed low diffraction intensity (I/σ = 8.54) despite multiple data sets from several recrystallizations. The molecule is plagued with positional disorder in the C(27-32) side chain, and all attempts to effectively model alternative sites for these atoms were unsuccessful. Without a successful model, the structure refinement can only afford reliable atom connectivity.
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