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. 2013 Feb 15;78(4):1682-6.
doi: 10.1021/jo302638v. Epub 2013 Feb 6.

Wacker-type oxidation of internal alkenes using Pd(Quinox) and TBHP

Ryan J DeLuca  1 , Jennifer L Edwards, Laura D Steffens, Brian W Michel, Xiaoxiao Qiao, Chunyin Zhu, Silas P Cook, Matthew S Sigman
Affiliations

Wacker-type oxidation of internal alkenes using Pd(Quinox) and TBHP

Ryan J DeLuca et al. J Org Chem. .

Abstract

The Pd-catalyzed TBHP-mediated Wacker-type oxidation of internal alkenes is reported. The reaction uses 2-(4,5-dihydro-2-oxazolyl)quinoline (Quinox) as ligand and TBHP(aq) as oxidant to deliver single ketone constitutional isomer products in a predictable fashion from electronically biased olefins. This methodology is showcased through its application on an advanced intermediate in the total synthesis of the antimalarial drug artemisinin.

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Figures

Figure 1
Figure 1
Previously reported Wacker oxidations using electronically biased internal alkenes.
Scheme 1
Scheme 1
The TBHP-Mediated Wacker Oxidation Provides Access to 15, an Intermediate in the Synthesis of Natural Product Artemisinin.
See this image and copyright information in PMC

References

    1. Keith JA, Henry PM. Angew. Chem. Int. Ed. 2009;48:9038. - PubMed
    2. Cornell CN, Sigman MS. Inorg. Chem. 2007;46:1903. - PubMed
    3. Takacs JM, Jiang X.-t. Curr. Org. Chem. 2003;7:369.
    4. Tsuji J. Synthesis. 1984;369
    1. Morandi B, Wickens ZK, Grubbs RH. Angew. Chem., Int. Ed. 2013 DOI: 10.1002/anie.201209541. - PubMed
    2. Gaunt MJ, Yu J, Spencer JB. Chem. Commun. 2001;1844 - PubMed
    3. Nelson DJ, Li R, Brammer C. J. Am. Chem. Soc. 2001;123:1564. - PubMed
    4. Betzemeier B, Lhermitte F. d. r., Knochel P. Tetrahedron Lett. 1998;39:6667.
    5. Okota T, Fujibayashi S, Nishiyama Y, Sakaguchi S, Ishii Y. J. Mol. Catal. A: Chem. 1996;114:113.
    6. Kang S-K, Jung K-Y, Chung J-U, Namkoong E-Y, Kim T-H. J. Org. Chem. 1995;60:4678.
    7. Sommovigo M, Alper H. J. Mol. Catal. 1994;88:151.
    8. Hosokawa T, Nakahira T, Takano M, Murahashi S-I. J. Mol. Catal. 1992;74:489.
    9. Miller DG, Wayner DDM. Can. J. Chem. 1992;70:2485.
    10. Kulkarni MG, Sebastian MT. Synth. Commun. 1991;21:581.
    11. Miller DG, Wayner DDM. J. Org. Chem. 1990;55:2924.
    12. Takehira K, Hayakawa T, Orita H, Shimizu M. J. Mol. Catal. 1989;53:15.
    13. Grattan TJ, Whitehurst JS. J. Chem. Soc., Chem. Commun. 1988;43
    14. Akermark B, Soederberg BC, Hall SS. Organometallics. 1987;6:2608.
    15. Takehira K, Orita H, Oh IH, Leobardo CO, Martinez GC, Shimidzu M, Hayakawa T, Ishikawa T. J. Mol. Catal. 1987;42:247.
    16. Tsuji J, Minato M. Tetrahedron Lett. 1987;28:3683.
    17. Keinan E, Seth KK, Lamed R. J. Am. Chem. Soc. 1986;108:3474.
    18. Zahalka HA, Januszkiewicz K, Alper H. J. Mol. Catal. 1986;35:249.
    19. Alper H, Januszkiewicz K, Smith DJH. Tetrahedron Lett. 1985;26:2263.
    20. Takehira K, Hayakawa T, Orita H. Chem. Lett. 1985;14:1835.
    21. Ogawa H, Fujinami H, Taya K, Teratani S. Bull. Chem. Soc. Jpn. 1984;57:1908.
    1. Tsuji J, Nagashima H, Hori K. Tetrahedron Lett. 1982;23:2679.
    2. Tsuji J, Nagashima H, Hori K. Chem. Lett. 1980;9:257.
    1. Weiner B, Baeza A, Jerphagnon T, Feringa BL. J. Am. Chem. Soc. 2009;131:9473. - PubMed
    1. Mitsudome T, Mizumoto K, Mizugaki T, Jitsukawa K, Kaneda K. Angew. Chem. Int. Ed. 2010;49:1238. - PubMed

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