Alkane desaturation by concerted double hydrogen atom transfer to benzyne

Nature

Volumn 501, Issue 7468, 2013, Pages 531-534

  Niu, Dawen ^a   Willoughby, Patrick H ^a   Woods, Brian P ^a   Baire, Beeraiah ^a   Hoye, Thomas R ^a  

^a UNIVERSITY OF MINNESOTA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKANE; ALKYNE; BENZYNE; HYDROCARBON; HYDROGEN; TRIYNE; UNCLASSIFIED DRUG;

ALKANE; GEOMETRY; HYDROCARBON; HYDROGEN;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; DIELS ALDER REACTION; FATTY ACID DESATURATION; HYDROGEN BOND; ISOMERIZATION; PRIORITY JOURNAL;

ALKANES; ALKENES; BENZENE DERIVATIVES; CYCLIZATION; HYDROGEN; HYDROGEN BONDING; HYDROGENATION; ISOMERISM; OXIDATION-REDUCTION;

EID: 84885623768     PISSN: 00280836     EISSN: 14764687     Source Type: Journal    
DOI: 10.1038/nature12492     Document Type: Article

References (27)

1. Linstead, R. P., Braude, E. A., Mitchell, P. W. D.,Wooldridge, K. R. H.& Jackman, L. M. Transfer of hydrogen in organic systems. Nature 169, 100-103 (1952).
2. Bloomfield, D. K. & Bloch, K. The formation of D9-unsaturated fatty acids. J. Biol. Chem. 235, 337-345 (1960).
3. Buist, P. H. Fatty acid desaturases: selecting the dehydrogenation channel. Nat. Prod. Rep. 21, 249-262 (2004).
4. Bhattacharya, A. et al. Characterization of the fungal gibberellin desaturase as a 2-oxoglutarate-dependent dioxygenase and its utilization for enhancing plant growth. Plant Physiol. 160, 837-845 (2012).
5. Moran, N. A. & Jarvik, T. Lateral transfer of genes from fungi underlies carotenoid production in aphids. Science 328, 624-627 (2010).
6. Hoye, T. R., Baire, B., Niu, D., Willoughby, P. H. & Woods, B. P. The hexadehydro-Diels-Alder reaction. Nature 490, 208-212 (2012).
7. Hoffmann, R. W. Dehydrobenzene and Cycloalkynes (Organic Chemistry Vol. 11) (Academic, 1967).
8. Tadross, P. M. & Stoltz, B. M. A comprehensive history of arynes in natural product total synthesis. Chem. Rev. 112, 3550-3577 (2012).
9. Baire, B., Niu, D., Willoughby, P. H., Woods, B. P. & Hoye, T. R. Synthesis of complex benzenoids via the intermediate generation of o-benzynes through the hexadehydro-Diels-Alder reaction. Nature Protocols 8, 501-508 (2013).
10. Miyawaki, K., Suzuki, R., Kawano, T. & Ueda, I. Cycloaromatization of a nonconjugated polyenyne system: synthesis of 5H-benzo[d]fluoreno[3,2-b]pyrans via diradicals generated from 1-[2-{4-(2-alkoxymethylphenyl)butan-1,3-diynyl}] phenylpentan-2,4-diyn-l-ols and trapping evidence for the 1,2-didehydrobenzene diradical. Tetrahedr. Lett. 38, 3943-3946 (1997).
11. Bradley, A. Z. & Johnson, R. P. Thermolysis of 1,3,8-nonatriyne: evidence for intramolecular [214] cycloaromatization to a benzyne intermediate. J.Am. Chem. Soc. 119, 9917-9918 (1997).
12. Ajaz, A. et al. Concerted vs. stepwise mechanisms in dehydro-Diels-Alder reactions. J. Org. Chem. 76, 9320-9328 (2011).
13. Hoffmann, R. W. & Suzuki, K. A 'hot, energized' benzyne. Angew. Chem. Int. Ed. 52, 2-4 (2013).
14. Yun, S. Y., Wang, K.-P., Lee, N.-K., Mamidipalli, P. & Lee, D. Alkane C-H insertion by aryne intermediates with a silver catalyst. J. Am. Chem. Soc. 135, 4668-4671 (2013).
15. Voica, A.-F., Mendoza, A., Gutekunst, W. R., Fraga, J. O. & Baran, P. S. Guided desaturation of unactivated aliphatics. Nature Chem. 4, 629-635 (2012).
16. Tsui, J. A. & Sterenberg, B. T. A metal-templated 412 cycloaddition reaction of an alkyne and a diyne to form a 1,2-aryne. Organometallics 28, 4906-4908 (2009).
17. de Almeida, G., Townsend, L. C. & Bertozzi, C. R. Synthesis and reactivity of dibenzoselenacycloheptynes. Org. Lett. 15, 3038-3041 (2013).
18. Hünig, S.,Müller, H.&Thier, W.Reduktionenmit diimid. Tetrahedr. Lett. 2,353-357 (1961).
19. Corey, E. J., Pasto, D. J. & Mock, W. L. Chemistry of diimide. II. Stereochemistry of hydrogen transfer to carbon-carbon multiple bonds. J. Am. Chem. Soc. 83, 2957-2958 (1961).
20. Fernández, I., Coss?́o, F. P. & Sierra, M. A. Dyotropic reactions: mechanisms and synthetic applications. Chem. Rev. 109, 6687-6711 (2009).
21. Fernández, I., Sierra, M. A. & Coss?́o, F. P. In-plane aromaticity in double-group transfer reactions. J. Org. Chem. 72, 1488-1491 (2007).
22. Hoye, T. R., Eklov, B. M., Ryba, T. D., Voloshin, M. & Yao, L. J. No-D NMR (no deuterium proton NMR) spectroscopy: a simple yet powerful method for analyzing reaction and reagent solutions. Org. Lett. 6, 953-956 (2004).
23. Himeshima, Y., Sonoda, T. & Kobayashi, H. Fluoride-induced 1,2-elimination of o-trimethylsilylphenyl triflate to benzyne under mild conditions. Chem. Lett. 12, 1211-1214 (1983).
24. Ma, Z.-X., Feltenberger, J. B. & Hsung, R. P. Total syntheses of chelidonine and norchelidonine via an enamide-benzyne-[212] cycloaddition cascade. Org. Lett. 14, 2742-2745 (2012).
25. Sumida, Y., Kato, T. & Hosoya, T. Generation of arynes via ate complexes of arylboronic esters with an ortho-leaving group. Org. Lett. 15, 2806-2809 (2013).
26. Davies, H. M. L., Du Bois, J. & Yu, J.-Q. C-H functionalization in organic synthesis. Chem. Soc. Rev. 40, 1855-1856 (2011).
27. Paul, G. F., Jak, B. & Lankin, D. A. Routine experimental protocol for qHNMR illustrated with taxol. J. Nat. Prod. 70, 589-595 (2007).