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Volumn 69, Issue 8, 2004, Pages 2750-2754

Simple Thiazocine-2-acetic Acid Derivatives via Ring-Closing Metathesis

Author keywords

[No Author keywords available]

Indexed keywords

ADDITION REACTIONS; DERIVATIVES; OLEFINS; OXIDATION; SULFUR COMPOUNDS; SYNTHESIS (CHEMICAL);

EID: 1842689070     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo035692z     Document Type: Article
Times cited : (29)

References (101)
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    • For a review of the difficulties of medium size ring synthesis via standard cyclization methodologies, see: Illuminati, G. Acc. Chem. Res. 1981, 14, 95. Following the general trend for cyclane formation (Eliel, E. L.; Wilen, S. H.; Mander, L. N. Stereochemistry of Organic Compounds; Wiley-Interscience: New York, NY, 1994; pp 678-684) cyclic thialkanes and thiazalkanes (MaGee, D. I.; Beck, E. J. J. Org. Chem. 2000, 65, 8367-8371) containing eight- or nine-membered rings form in very low yield by treatment of the corresponding alkyl dibromides with sodium sulfide nonahydrate. Some simple cyclic 1,4-thiazepines are available from tetrahydrothiopyran-4-one (Beckmann rearrangement of the derived oxime followed by amide reduction) (Doi, J. T.; Musker, W. K.; deLeeuw, D. L.; Hirschon, A. S. J. Org. Chem. 1981, 46, 1239-1243), and eight-, nine-, and ten-ring atom oxathiacycloalkenes are available by ring expansion of halo-O,S-acetals (Coster, M. J.; DeVoss, J. J. Org. Lett. 2002, 4, 3047-3050.).
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    • 4 was added to the RCM reaction according to Fuerstner's protocol (Fuerstner, A.; Langemann, K. J. Am. Chem. Soc. 1997, 119, 9130-9136) and both S-oxidized counterparts to the sulfide (3 and 4) readily undergo RCM]. The problem is more likely due to inactivation of the catalyst by coordination of the Ru to S(II). Coordination/inactivation could occur intermolecularly prior to interaction of the Ru with the olefinic sites or intramolecularly, perhaps as shown in structure i. The latter process (involving coordination of ruthenium to hydroxyl oxygen via a six-membered ring rather than the eight-membered ring as in i) has been suggested previously (for example, Washburn, D. G.; Heidebrecht, R. W.; Martin, S. F. Org. Lett. 2003, 5, 3523-3525) to explain Grubbs' catalyst inactivation. This process seems less likely in the present context because of the size of the ring involved and the necessity to invoke selective reaction of the N-allylic olefinic site, even though the S-allylic olefinic site is sterically and electronically similar.
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    • 4 was added to the RCM reaction according to Fuerstner's protocol (Fuerstner, A.; Langemann, K. J. Am. Chem. Soc. 1997, 119, 9130-9136) and both S-oxidized counterparts to the sulfide (3 and 4) readily undergo RCM]. The problem is more likely due to inactivation of the catalyst by coordination of the Ru to S(II). Coordination/inactivation could occur intermolecularly prior to interaction of the Ru with the olefinic sites or intramolecularly, perhaps as shown in structure i. The latter process (involving coordination of ruthenium to hydroxyl oxygen via a six-membered ring rather than the eight-membered ring as in i) has been suggested previously (for example, Washburn, D. G.; Heidebrecht, R. W.; Martin, S. F. Org. Lett. 2003, 5, 3523-3525) to explain Grubbs' catalyst inactivation. This process seems less likely in the present context because of the size of the ring involved and the necessity to invoke selective reaction of the N-allylic olefinic site, even though the S-allylic olefinic site is sterically and electronically similar.
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    • Gladysz and co-workers have reported use of a cationic rhenium compound that serves both as a protecting group for S(II) and RCM catalyst for thioethers: Martin-Alvarez, J. M.; Hampel, F.; Arif, A. M.; Gladysz, J. A. Organometallics 1999, 18, 955-957.
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