Iterative stereospecific reagent-controlled homologation of pinacol boronates by enantioenriched α-chloroalkyllithium reagents

Journal of the American Chemical Society

Volumn 129, Issue 11, 2007, Pages 3068-3069

  Blakemore, Paul R ^a   Burge, Matthew S ^a  

^a OREGON STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYL GROUP; BORON DERIVATIVE; CARBENOID; CHLORINE; LIGAND; LITHIUM DERIVATIVE; ORGANOMETALLIC COMPOUND; REAGENT; SULFIDE; SULFOXIDE;

ARTICLE; CHEMICAL REACTION KINETICS; CHEMICAL STRUCTURE; CHIRALITY; COMPLEX FORMATION; CRYSTALLIZATION; DIASTEREOISOMER; ENANTIOMER; HIGH PERFORMANCE LIQUID CHROMATOGRAPHY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; PINACOL REARRANGEMENT; STEREOCHEMISTRY; STEREOSPECIFICITY; SYNTHESIS;

EID: 33947430499     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja068808s     Document Type: Article

References (21)

1. (a) Fields, G. B. Solid Phase Peptide Synthesis; Academic Press: San Diego, 1997.
2. (b) Smith, K., Ed. Solid Supports and Catalysts in Organic Synthesis; Ellis Horwood: New York, 1992.
3. The Negishi ZACA reaction and Matteson's asymmetric chain extension process (an antecedent of the work herein) represent two of the most versatile iterative C-C bond-forming reactions currently available; see: (a) Liang, B.; Novak, T.; Tan, Z.; Negishi, E. J. Am. Chem. Soc. 2006, 128, 2770 and refs therein.
4. (b) Matteson, D. S. Tetrahedron 1998, 54, 10555.
5. Blakemore, P. R.; Marsden, S. P.; Vater, H. D. Org. Lett. 2006, 8, 773.
6. For illuminating discourse on 1,2-metalate rearrangements from borate complexes, see: Aggarwal, V. K.; Fang, G. Y.; Ginesta, X.; Howells, D. M.; Zaja, M. Pure Appl. Chem. 2006, 78, 215.
7. (a) Hoffmann, R. W.; Nell, P. G.; Leo, R.; Harms, K. Chem. Eur. J. 2000, 6, 3359.
8. (b) Hoffmann, R. W. Chem. Soc. Rev. 2003, 32, 225.
9. Matteson, D. S.; Mah, R. W. H. J. Am. Chem. Soc. 1963, 85, 2599.
10. Satoh, T.; Takano, K. Tetrahedron 1996, 52, 2349.
11. Blakemore, P. R.; Burge, M. S. Presented in part at the 232nd ACS National Meeting, San Francisco, CA, September 10-14; American Chemical Society: Washington, D.C., 2006; paper ORGN 353.
12. (a) Drago, C.; Caggiano, L.; Jackson, R. F. W. Angew. Chem., Int. Ed. 2005, 44, 7221.
13. (b) Cogan, D. A.; Liu, G.; Kim, K.; Backes, B. J.; Ellman, J. A. J. Am. Chem. Soc. 1998, 120, 8011.
14. Bolm, C.; Bienewald, F. Angew. Chem., Int. Ed. Engl. 1995, 34, 2640.
15. Satoh, T.; Oohara, T.; Ueda, Y.; Yamakawa, K. Tetrahedron Lett. 1988, 29, 313.
16. Blakemore, P. R.; Burge, M. S. Unpublished results.
17. 2 = Me) gave the corresponding exchange product in only 50% yield together with 25% of recovered partially epimerized starting material (syn:anti = 52:48).
18. (a) Sadhu, K. M.; Matteson, D. S. Organometallics 1985, 4, 1687.
19. (b) Soundararajan, R.; Li, G.; Brown, H. C. Tetrahedron Lett. 1994, 35, 8957.
20. See Supporting Information for details.
21. For an introduction to this type of "statistical enantiomeric amplification" phenomenon, see: Negishi, E. Dalton Trans. 2005, 827.