A new copper-catalyzed [3 + 2] cycloaddition: Enantioselective coupling of terminal alkynes with azomethine imines to generate five-membered nitrogen heterocycles

Journal of the American Chemical Society

Volumn 125, Issue 36, 2003, Pages 10778-10779

  Shintani, Ryo ^a   Fu, Gregory C ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

3 ACETYL 7 [2 (2 AMINO 4 THIAZOLYL) 2 METHOXYIMINOACETAMIDO] 8 OXO 1,5 DIAZABICYCLO[3.3.0]OCT 2 ENE 2 CARBOXYLIC ACID; ALKYNE DERIVATIVE; ANTIINFECTIVE AGENT; AZOMETHINE YLIDE; COPPER; HETEROCYCLIC AMINE; IMINE;

ARTICLE; CATALYSIS; CYCLOADDITION; DRUG STRUCTURE; DRUG SYNTHESIS; ENANTIOSELECTIVITY; REACTION ANALYSIS; ROOM TEMPERATURE; STRUCTURE ANALYSIS;

ALKYNES; AZO COMPOUNDS; CATALYSIS; COPPER; CYCLIZATION; HETEROCYCLIC COMPOUNDS; IMINES; STEREOISOMERISM;

EID: 0042234004     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja036922u     Document Type: Article

References (30)

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19. The pyrazolidinone ring serves as a surrogate for the β-lactam unit that is a common feature of many antibiotics. For an overview of the chemistry and biology of LY186826, see: (a) Ternansky, R. J.; Holmes, R. A. Drugs Future 1990, 15, 149-157. (b) Ternansky, R. J.; Draheim, S. E. In Recent Advances in the Chemistry of β-Lactam Antibiotics; Bentley, P. H., Southgate, R. H., Eds.; Royal Society of Chemistry: London, 1989; pp 139-156. (c) Jungheim, L. N. ; Sigmund, S. K. J. Org. Chem. 1987, 52, 4007-4013. In contrast to LY186826, which is a [3.3.0]-fused (⇒-carbapenem analogue) pyrazolidinone, monocyclic (⇒ monobactam analogue) or [4.3.0]-fused (⇒ carbacephem analogue) pyrazolidinones do not show biological activity.
20. The pyrazolidinone ring serves as a surrogate for the β-lactam unit that is a common feature of many antibiotics. For an overview of the chemistry and biology of LY186826, see: (a) Ternansky, R. J.; Holmes, R. A. Drugs Future 1990, 15, 149-157. (b) Ternansky, R. J.; Draheim, S. E. In Recent Advances in the Chemistry of β-Lactam Antibiotics; Bentley, P. H., Southgate, R. H., Eds.; Royal Society of Chemistry: London, 1989; pp 139-156. (c) Jungheim, L. N. ; Sigmund, S. K. J. Org. Chem. 1987, 52, 4007-4013. In contrast to LY186826, which is a [3.3.0]-fused (⇒-carbapenem analogue) pyrazolidinone, monocyclic (⇒ monobactam analogue) or [4.3.0]-fused (⇒ carbacephem analogue) pyrazolidinones do not show biological activity.
21. For example, the addition of CHIRAPHOS, DUPHOS, or JOSIPHOS leads to a low yield of heterocycle 4.
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24. The 1,3-dipolar cycloaddition also proceeds cleanly in the presence of (-)-sparteine and a pybox ligand, albeit in lower ee.
25. (a) Shintani, R.; Lo, M. M.-C.; Fu, G. C. Org. Lett. 2000, 2, 3695-3697.
26. (b) Shintani, R.; Fu, G. C. Org. Lett. 2002, 4, 3699-3702.
27. (c) Reference 5b.
28. Unless otherwise noted, we detect none of the other regioisomer in these copper-catalyzed dipolar cycloadditions.
29. 2NEt). (4) CuBr, CuCl, and Cu(OTf) furnish comparable yield, but lower ee. (5) When the cycloaddition is conducted on a 4.0 mmol scale, the desired product is isolated in 97% yield (1.06 g) and with 84% ee. Ligand 6a is recovered in 78% yield.
30. Higher regioselectivity-at the expense of reaction rate-can be obtained by conducting the cycloadditions at room temperature.