Transmetalation of Alkylboranes to Palladium in the Suzuki Coupling Reaction Proceeds with Retention of Stereochemistry

Journal of Organic Chemistry

Volumn 63, Issue 3, 1998, Pages 458-460

  Ridgway, Brian H ^a   Woerpel, K A ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000311321     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo970803d     Document Type: Article

References (22)

1. Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457-2483.
2. See, for example: Johnson, C. R.; Braun, M. P. J. Am. Chem. Soc. 1993, 115, 11014-11015.
3. Hatanaka, Y.; Hiyama, T. J. Am. Chem. Soc. 1990, 112, 7793-7794.
4. Labadie, J. W.; Stille, J. K. J. Am. Chem. Soc. 1983, 105, 6129-6137.
5. Ye, J.; Bhatt, R. K.; Falck, J. R. J. Am. Chem. Soc. 1994, 116, 1-5.
6. Falck, J. R.; Bhatt, R. K.; Ye, J. J. Am. Chem. Soc. 1995, 117, 5973-5982.
7. Cyclopropylboranes with alkyl substituents trans to the boron undergo coupling to provide trans products. This observation indicates that transmetalation may occur with retention of configuration, although coupling with cis-substituted Cyclopropylboranes was not investigated: (a) Wang, X.-Z.; Deng, M.-Z. J. Chem. Soc., Perkin Trans. 1 1996, 2663-2664. (b) Hildebrand, J. P.; Marsden, S. P. Synlett 1996, 893-894. Charette, A. B.; De Freitas-Gil, R. P. Tetrahedron Lett. 1997, 38, 2809-2812.
8. Cyclopropylboranes with alkyl substituents trans to the boron undergo coupling to provide trans products. This observation indicates that transmetalation may occur with retention of configuration, although coupling with cis-substituted Cyclopropylboranes was not investigated: (a) Wang, X.-Z.; Deng, M.-Z. J. Chem. Soc., Perkin Trans. 1 1996, 2663-2664. (b) Hildebrand, J. P.; Marsden, S. P. Synlett 1996, 893-894. Charette, A. B.; De Freitas-Gil, R. P. Tetrahedron Lett. 1997, 38, 2809-2812.
9. Cyclopropylboranes with alkyl substituents trans to the boron undergo coupling to provide trans products. This observation indicates that transmetalation may occur with retention of configuration, although coupling with cis-substituted Cyclopropylboranes was not investigated: (a) Wang, X.-Z.; Deng, M.-Z. J. Chem. Soc., Perkin Trans. 1 1996, 2663-2664. (b) Hildebrand, J. P.; Marsden, S. P. Synlett 1996, 893-894. Charette, A. B.; De Freitas-Gil, R. P. Tetrahedron Lett. 1997, 38, 2809-2812.
10. Knochel has recently demonstrated that transmetalation of a secondary alkyl group from boron to zinc occurs with retention of configuration: Micouin, L.; Oestreich, M.; Knochel, P. Angew. Chem., Int. Ed. Engl. 1997, 36, 245-246.
11. Soderquist has recently presented a similar strategy to the one reported here and has arrived at the same conclusion: Soderquist, J. A.; Rane, A.; Matos, K. Presented at the 213th National Meeting of the American Chemical Society, San Francisco, CA, April 1997; paper ORGN 582. Matos, K.; Soderquist, J. A. J. Org. Chem. 1997, 63, 461-470.
12. Soderquist has recently presented a similar strategy to the one reported here and has arrived at the same conclusion: Soderquist, J. A.; Rane, A.; Matos, K. Presented at the 213th National Meeting of the American Chemical Society, San Francisco, CA, April 1997; paper ORGN 582. Matos, K.; Soderquist, J. A. J. Org. Chem. 1997, 63, 461-470.
13. Whitesides pioneered the use of similarly deuterated substrates to evaluate the stereochemical course of reactions involving alkylmetal compounds: Bock, P. L.; Boschetto, D. M.; Rasmussen, J. R.; Demers, J. P.; Whitesides, G. M. J. Am. Chem. Soc. 1974, 96, 2814-2825.
14. Johnson, C. R.; Adams, J. P.; Braun, M. P.; Senanayake, C. B. W.; Wovkulich, P. M.; Uskakovic, M. R. Tetrahedron Lett. 1992, 33, 917-918.
15. 2H} NMR spectra showed coupling constants similar to these values (6.1 and 9.2 Hz, for syn-7 and anti-8, respectively). Variable-temperature NMR experiments also indicated only minor changes in the spectral data. At -50°C, the coupling constant for syn-7 decreased; this resonance became a broad singlet. At this temperature, the coupling constant for anti-8 increased slightly to 9.3 Hz.
16. A similar analysis has been used to determine the stereochemistry of polydeuterated alkanes: Gilchrist, J. H.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 12021-12028.
17. Kabalka, G. W.; Bowman, N. S. J. Org. Chem. 1973, 38, 1607-1608.
18. Milstem, D.; Stille, J. K. J. Am. Chem. Soc. 1979, 101, 4981-4991.
19. The details of the preparation and characterization of this compound are provided as Supporting Information.
20. The combustion analysis data did not differentiate deuterium and hydrogen in the evolved water. Therefore, the calculated hydrogen analyses were determined by dividing the combined masses of the hydrogen atoms (as if they were all protons) by the formula weight of the deuterated compound.
21. Kautzner, B.; Wailes, P. C.; Weigold, H. J. Chem. Soc., Chem. Commun. 1969, 1105.
22. For a recent example of reactions of Schwartz's reagent with alkynes, see: Lipshutz, B. H.; Keil, R.; Ellsworth, E. L. Tetrahedron Lett. 1990, 31, 7257-7260.