A hypervalent iodide-initiated fragment coupling cascade of N-allylhydrazones

Angewandte Chemie - International Edition

Volumn 50, Issue 19, 2011, Pages 4437-4440

  Lutz, Kelly E ^a   Thomson, Regan J ^a  

^a NORTHWESTERN UNIVERSITY   (United States)

Author keywords

cascade reactions; hydrazones; hypervalent iodide reagents; stereoselective synthesis

Indexed keywords

CASCADE PROCESS; CASCADE REACTIONS; DIVERSE RANGE; FRAGMENT COUPLING; FUNCTIONALIZED; HYDRAZONES; HYPERVALENT IODIDE REAGENTS; NATURAL PRODUCTS; STEREOCENTERS; STEREOSELECTIVE SYNTHESIS;

ALDEHYDES; ETHERS; OLEFINS; ORGANIC COMPOUNDS;

STEREOSELECTIVITY;

ALCOHOL DERIVATIVE; ALDEHYDE; HYDRAZONE DERIVATIVE; IODIDE;

ARTICLE; CHEMISTRY; STEREOISOMERISM;

ALCOHOLS; ALDEHYDES; HYDRAZONES; IODIDES; STEREOISOMERISM;

EID: 79955495941     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201100888     Document Type: Article

References (23)

1. E. J. Corey, X.-M. Cheng, The Logic of Chemical Synthesis, Wiley, New York, 1989.
2. D. A. Mundal, J. J. Lee, R. J. Thomson, J. Am. Chem. Soc. 2008, 130, 1148-1149
3. D. A. Mundal, K. E. Lutz, R. J. Thomson, Org. Lett. 2009, 11, 465-468
4. D. A. Mundal, C. A. Avetta, Jr., R. J. Thomson, Nat. Chem. 2010, 2, 294-297.
5. The thermal rearrangement of N-allylhydrazones was first reported by Stevens and co-workers in 1973, see:, R. V. Stevens, E. E. McEntire, W. E. Barnett, E. Wenkert, J. Chem. Soc. Chem. Commun. 1973, 662-663.
6. For reviews regarding the chemistry of hypervalent iodide reagents, see
7. R. M. Moriarty, R. K. Vaid, Synthesis 1991, 431-447
8. A. Varvoglis, The Organic Chemistry of Polycoordinated Iodine, VCH, New York, 1992
9. V. V. Zhdankin, P. J. Stang, Chem. Rev. 2008, 108, 5299-5358
10. V. V. Zhdankin, P. J. Stang, Chem. Rev. 2002, 102, 2523-2584
11. P. J. Stang, V. V. Zhdankin, Chem. Rev. 1996, 96, 1123-1178.
12. N. S. Zefirov, S. O. Safronov, A. A. Kaznacheev, V. V. Zhdankin, Zh. Org. Khim. 1989, 25, 1807-1808.
13. The effect of counter-ions in some hypervalent iodide-mediated transformations has been reported, see:, V. V. Zhdankin, R. Tykwinski, B. Berglund, M. Mullikin, R. Caple, N. S. Zefirov, A. S. Koz'min, J. Org. Chem. 1989, 54, 2609-2612.
14. G. C. Fu, R. H. Grubbs, J. Am. Chem. Soc. 1992, 114, 5426-5427.
15. 1H NMR coupling constants. See Supporting Information.
16. The syn configuration was determined through direct comparison to an authentic sample prepared using the well established syn-selective crotylation of aldehydes developed by Roush and co-workers, see:, W. R. Roush, K. Ando, D. B. Powers, A. D. Palkowitz, R. L. Halterman, J. Am. Chem. Soc. 1990, 112, 6339-6348. See Supporting Information for full details. Substrates 13 h and 13 i were assigned by analogy.
17. The requisite hydrazine required for the formation of enantioenriched hydrazone 12 e was prepared through an enantioselective α-amination of 3-methylbutanal according to the procedure of List for related aldehydes, see;, B. List, J. Am. Chem. Soc. 2002, 124, 5656-5657. See Supporting Information for full details.
18. Prepared by using a variant of the Pd-catalyzed allylation reported by Trost and Du Bois, see:, B. M. Trost, S. Malhotra, D. E. Olson, A. Maruniak, J. Du Bois, J. Am. Chem. Soc. 2009, 131, 4190-4191. See Supporting Information for full details.
19. The relative and absolute configuration of 19 was determined through a chemical correlation. See Supporting Information for full details.
20. Asymmetric induction in sigmatropic rearrangements was first reported for the Cope rearrangement by Hill and Gilman, see:, R. K. Hill, N. W. Gilman, J. Chem. Soc. Chem. Commun. 1967, 619-620.
21. For a review of allylic strain as a controlling element in chemical transformations, see:, R. W. Hoffmann, Chem. Rev. 1989, 89, 1841-1860.
22. The term "natural product-like" is used in fields such as chemical biology to describe scaffolds that have structural features related to natural products, see:, A. M. Boldi, Curr. Opin. Chem. Biol. 2004, 8, 281-286.
23. Attempts to use enantiopure chiral alcohols to directly induce stereoselectivity during the C-O bond-forming step using achiral hydrazone precursors only ever led to 1:1 mixtures of diastereomers.