Animation, aminocarbonylation, and alkoxycarbonylation of allenic/propargylic Pd intermediates derived from nonracemic propargylic mesylates: Synthesis of nonracemic propargyl amines, allenic amides, and butenolides

Journal of Organic Chemistry

Volumn 61, Issue 10, 1996, Pages 3238-3239

  Marshall, James A ^a   Wolf, Mark A ^a  

^a UNIVERSITY OF VIRGINIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALLENE DERIVATIVE; BUTENOLIDE;

ARTICLE; DRUG SYNTHESIS; REACTION ANALYSIS; TECHNIQUE;

EID: 0029996546     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo960442m     Document Type: Article

References (20)

1. Marshall, J. A.; Wallace, E. M. J. Org. Chem. 1995, 60, 796.
2. 4 gives the acids directly but proceeds in low to moderate yield.
3. For aminations of π-allyl palladium species with aliphatic amines see, (a) Báckvall, J-E.; Nordberg, R. E.; Zetterberg, K.; Akermark, B. Organometallics 1983, 2, 1625. (b) Baer, H. H.; Hanna, Z. S. Can. J Chem. 1981, 59, 889. (c) Trost, B. M.; Keinan, E. J. Org. Chem. 1979, 44, 3451.
4. For aminations of π-allyl palladium species with aliphatic amines see, (a) Báckvall, J-E.; Nordberg, R. E.; Zetterberg, K.; Akermark, B. Organometallics 1983, 2, 1625. (b) Baer, H. H.; Hanna, Z. S. Can. J Chem. 1981, 59, 889. (c) Trost, B. M.; Keinan, E. J. Org. Chem. 1979, 44, 3451.
5. For aminations of π-allyl palladium species with aliphatic amines see, (a) Báckvall, J-E.; Nordberg, R. E.; Zetterberg, K.; Akermark, B. Organometallics 1983, 2, 1625. (b) Baer, H. H.; Hanna, Z. S. Can. J Chem. 1981, 59, 889. (c) Trost, B. M.; Keinan, E. J. Org. Chem. 1979, 44, 3451.
6. These amines were analyzed as their 3,5-dinitrobenzamide derivatives on a (R,R)-Whelk-O column.
7. Tsuji, J.; Mandai, T. Angew. Chem., Int. Ed. Engl. 1995, 34, 2589.
8. Marshall, J. A.; Xie, S. J. Org. Chem. 1995, 60, 7230. Ku, Y. Y; Patel, R. R.; Elisseou, E. M.; Sawick, D. P. Tetrahedron Lett. 1995, 36, 2733.
9. Marshall, J. A.; Xie, S. J. Org. Chem. 1995, 60, 7230. Ku, Y. Y; Patel, R. R.; Elisseou, E. M.; Sawick, D. P. Tetrahedron Lett. 1995, 36, 2733.
10. N2′ attack by the amine on this allenyl Pd intermediate Cf. Elsevier, C. J.; Stehouwer, P. M.; Westmijze, H.; Vermeer, P. J. Org Chem. 1983, 48, 1103. Alternatively, the amine and CO may discriminate between equilibrating allenyl and propargyl Pd intermediates.
11. Cf. Marshall, J. A.; Wang, X-j. J. Org. Chem. 1991, 56, 3211.
12. Cf. Smith, A. B., III.; Duan, J. J.-W.; Hull, K. G.; Salvatore, B. A. Tetrahedron Lett. 1991, 32, 4855.
13. 5
14. β-TMS ethyl esters have rarely been employed in iodolactonizations. Considering the facile transformation of esters 7.1a and 7.1b to iodolactones 7.2a and 7.2b. it is likely that the methodology will be applicable to olefinic analogues, as well.
15. Baillargeon, V. P.; Stille, J. K. J. Am. Chem. Soc. 1986, 108, 452.
16. For a detailed study on the effect of Pd(0) concentration on racemization in π-allyl palladium intermediates, see Granberg, K. L.; Backvall, J.-E. J. Am. Chem. Soc. 1992, 114, 6858.
17. For recent alternative routes to butenolides, Cf. Trost, B. M.; Muller, T. J. J.; Martinez, J. J. Am Chem. Soc. 1995, 117, 1888. Hoye, T. R.; Humpal, P. E.; Jimenez, J. I.; Mayer, M. J.; Tan, L.; Ye, Z. Tetrahedron Lett. 1994, 35, 7517. Buchwald, S. L.; Fang, Q.; King, S. M. Tetrahedron. Lett. 1988, 29, 3445.
18. For recent alternative routes to butenolides, Cf. Trost, B. M.; Muller, T. J. J.; Martinez, J. J. Am Chem. Soc. 1995, 117, 1888. Hoye, T. R.; Humpal, P. E.; Jimenez, J. I.; Mayer, M. J.; Tan, L.; Ye, Z. Tetrahedron Lett. 1994, 35, 7517. Buchwald, S. L.; Fang, Q.; King, S. M. Tetrahedron. Lett. 1988, 29, 3445.
19. For recent alternative routes to butenolides, Cf. Trost, B. M.; Muller, T. J. J.; Martinez, J. J. Am Chem. Soc. 1995, 117, 1888. Hoye, T. R.; Humpal, P. E.; Jimenez, J. I.; Mayer, M. J.; Tan, L.; Ye, Z. Tetrahedron Lett. 1994, 35, 7517. Buchwald, S. L.; Fang, Q.; King, S. M. Tetrahedron. Lett. 1988, 29, 3445.
20. An inversion pathway has been established for additions of organozinc compounds to propargyl/allenyl Pd(II) intermediates leading to allenes. Elsevier, C. J.; Kleijn, H.; Boersma, J.; Vermeer, P. Organometallics 1986, 5, 716.