Suppressed β-hydride elimination in palladium-catalyzed cascade cyclization-coupling reactions: An efficient synthesis of 3-arylmethylpyrrolidines

Organic Letters

Volumn 2, Issue 9, 2000, Pages 1213-1215

  Lee, Chi Wan ^a   Oh, Kyung Seok ^a   Kim, Kwang S ^a   Ahn, Kyo Han ^a  

^a Pohang University of Science and Technology (POSTECH)   (South Korea)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0042092717     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0056426     Document Type: Article

References (28)

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14. 3, toluene, reflux, 91%.
15. 2 (ethyl acetate-hexane as eluant) gave 3-(4-fluorophenylmethyl)-4-methylene-N-(p-toluenesulfonyl)pyrrolidine in 92% yield (159 mg).
16. Notably, the combined yield of the two compounds is significantly different depending on the boronic acid used.
17. Because of the double bond isomerization, an isomeric mixture of Heck products was observed, which were inseparable on TLC.
18. The cascade cyclization-coupling reaction is different from the first example of the tandem Heck-Suzuki reaction reported by Shibasaki and co-workers (Kojuma, A.; Honzawa, S.; Boden, C. D. J.; Shibasaki, M. Tetrahedron Lett. 1997, 38, 3455-3458). In our case, the first step is not a complete Heck reaction but it involves a "Heck-type" carbopalladation intermediate.
19. The calculations were carried out at the HF/3-21G level using Gaussian 94 (Frisch et al. Gaussian 94; Gaussian Inc.: Pittsburgh, PA, 1995).
20. From the mixture, two major compounds were isolated and characterized by NMR and mass analysis. One of the products was assigned as the corresponding cascade reaction product (18% yield) and the other was tentatively assigned as the direct Suzuki coupling product (9% yield). In both products, an extensive double bond migration occurred probably due to the acetyl group, which resulted in a mixture of isomeric products.
21. For example, see: (a) de Meijere, A.; Bräse, S. J. Organomet. Chem. 1999, 576, 88-110.
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24. 1H NMR analysis of the mixture. The isolated yield of the mixture was 60% on the basis of the product ratio.
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