The thiopyran route to polypropionates: Enantioselective synthesis of membrenone B from racemic fragments

Journal of Organic Chemistry

Volumn 72, Issue 20, 2007, Pages 7805-7808

  Jheengut, Vishai ^a   Ward, Dale E ^a  

^a UNIVERSITY OF SASKATCHEWAN   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

DIASTEREOSELECTIVE; POLYPROPIONATES;

ENANTIOSELECTIVITY; REACTION KINETICS; SYNTHESIS (CHEMICAL);

ALCOHOLS;

1,4 DIOXA 8 THIASPIRO[4.5]DECANE 6 CARBOXYALDEHYDE; ALDEHYDE DERIVATIVE; MEMBRENONE B; POLYPROPIONATE DERIVATIVE; PROPIONIC ACID DERIVATIVE; TETRAHYDRO 4H THIOPYRAN 4 ONE; THIOPYRAN DERIVATIVE; UNCLASSIFIED DRUG;

ALDOL REACTION; ARTICLE; CHEMICAL REACTION KINETICS; ENANTIOSELECTIVITY; REACTION ANALYSIS; STEREOCHEMISTRY; SYNTHESIS;

PROPIONATES; PYRANS; PYRONES; STEREOISOMERISM; SULFHYDRYL COMPOUNDS;

EID: 34848827873     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo701546f     Document Type: Article

References (26)

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8. 4 reduction.
9. For a previous synthesis of ent-1 and ent-2, see ref 4c. For syntheses of 3 and (or) ent-3, see ref 4b and: (a) Marshall, J. A.; Ellis, K. C. Org. Lett. 2003, 5, 1729-1732.
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11. First aldol: (a) Ward, D. E.; Sales, M.; Man, C. C.; Shen, J.; Sasmal, P. K.; Guo, C. J. Org. Chem. 2002, 67, 1618-1629.
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15. (b) Ward, D. E.; Beye, G. E.; Sales, M.; Alarcon, I. Q.; Gillis, H. M.; Jheengut, V. J. Org. Chem. 2007, 72, 1667-1674.
16. (a) Ward, D. E.; Gillis, H. M.; Akinnusi, O. T.; Rasheed, M. A.; Saravanan, K.; Sasmal, P. K. Org. Lett. 2006, 8, 2631-2634.
17. (b) Ward, D. E.; Jheengut, V.; Beye, G. E. J. Org. Chem. 2006, 71, 8989-8992.
18. The configurations at the undefined stereocenters in 11 are not relevant because those centers become trigonal in 8.
19. For a more complete discussion and references on this phenomenon, see ref 8b.
20. The ss and as labels refer to the syn (s) or anti (a) relative configurations at C-3,1′ and C-1′,6′, respectively, in the diastereomers of 6 (and 10).
21. Consistent with that hypothesis, (S)-(-)-4 (50% yield; ca. 20% optical purity) was recovered from the reaction.
22. The racemic compounds have been described previously (ref 8a). For determination of the relative configurations for 12, 13, and 14, see ref 8b.
23. The alternative diastereomers would have a trans-fused tetrahydrothiopyrano[4,3-d] 1,3-dioxin ring system with a large group in an axial orientation.
24. 1H NMR) in the crude reaction mixtures consistent with the previous synthesis (ref 4c).
25. Ward, D. E.; Rasheed, M. A.; Gillis, H. M.; Beye, G. E.; Jheengut, V.; Achonduh, G. T. Synthesis 2007, 1584-1586.
26. See the Supporting Information.