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Fluoroalcohol-mediated reductive iodonio-Claisen rearrangement: Synthesis of complex ortho-substituted-allyl iodoarenes

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Abstract

Reductive iodonio-Claisen rearrangement (RICR) involving λ3-iodanes and allyl or substituted-allyl silanes in fluoroalcohols, such as 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) and 2,2,2-trifluoroethanol (TFE), was studied for the synthesis of complex ortho-allyl or substituted-allyl iodoarenes. In comparison to the previously reported condition involving boron trifluoride diethyl etherate, the RICR mediated by fluoroalcohols was found to proceed more effectively. The resulting complex ortho-allyl iodoarenes are useful synthetic intermediates and can be readily converted to various heterocyclic compounds.

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References

  1. Stang P J, Zhdankin V V. Organic polyvalent iodine compounds. Chemical Reviews. 1996, 96(3): 1123–1178

    Article  CAS  Google Scholar 

  2. Zhdankin V V, Stang P J. Recent developments in the chemistry of polyvalent iodine compounds. Chemical Reviews. 2002, 102(7): 2523–2584

    Article  CAS  Google Scholar 

  3. Zhdankin V V, Stang P J. Chemistry of polyvalent iodine. Chemical Reviews. 2008, 108(12): 5299–5358

    Article  CAS  Google Scholar 

  4. Ochiai M. Hypervalent halogans and their reactions in organic synthesis. Yakugaku Zasshi. Journal of the Pharmaceutical Society of Japan. 2009, 129(3): 321–334

    CAS  Google Scholar 

  5. Zhdankin V V. Hypervalent iodine (III) reagents in organic synthesis. ARKIVOC. 2009, 1(1): 1–62

    Google Scholar 

  6. Merritt E A, Olofsson B. α-Functionalization of carbonyl compounds using hypervalent iodine reagents. Synthesis (Stuttgart), 2011, 4: 517–538

    Google Scholar 

  7. Silva L F Jr, Olofsson B. Hypervalent iodine reagents in the total synthesis of natural products. Natural Product Reports. 2011, 28(10): 1722–1754

    Article  CAS  Google Scholar 

  8. Duschek A, Kirsch S F. 2-Iodoxybenzoic acid—a simple oxidant with a dazzling array of potential applications. Angewandte Chemie International Edition, 2011, 50(7): 1524–1552

    Article  CAS  Google Scholar 

  9. Duschek A, Kirsch S. For an overview of IBX-mediated oxidations. Angewandte Chemie. 2011, 123: 1562–1590

    Article  Google Scholar 

  10. Ochiai M, Ito T, Takaoka Y, Masaki Y. Generation of allenyliodinanes and their reductive iodonio-Claisen rearrangement. Journal of the American Chemical Society. 1991, 113(4): 1319–1323

    Article  CAS  Google Scholar 

  11. Ochiai M, Ito T, Masaki Y. Ipso selectivity in the reductive iodonio-Claisen rearrangement of allenyl(p-methoxyaryl)iodinanes. Journal of the Chemical Society. Chemical Communications. 1992, (1): 15–16

    Article  Google Scholar 

  12. Ochiai M, Ito T. Solvent effects on ipso versus ortho selectivity in the reductive iodonio-Claisen rearrangement of allenyl (p-methoxyphenyl) iodane. Journal of Organic Chemistry. 1995, 60(7): 2274–2275

    Article  CAS  Google Scholar 

  13. Ochiai M, Kida M, Okuyama T. On the mechanism of nucleophilic substitution of allenyl (aryl) iodine (III): Formation of propargyl cation and competition with Sigmatropic rearrangement. Tetrahedron Letters. 1998, 39(34): 6207–6210

    Article  CAS  Google Scholar 

  14. Gately D A, Luther T A, Norton J R, Miller M M, Anderson O P. Reaction of µ-oxobis [(trifluoromethanesulfonato)(phenyl) iodine (III)] with group 14 propargyl derivatives and a propargyl ether. Journal of Organic Chemistry. 1992, 57(24): 6496–6502

    Article  CAS  Google Scholar 

  15. Lee K, Kim D Y, Oh D Y. Reaction of allyltrimethylsilane with an aromatic compound using hypervalent organoiodine compound: A new allylation of aromatic compounds. Tetrahedron Letters. 1988, 29(6): 667–668

    Article  CAS  Google Scholar 

  16. Van De Water R W, Hoarau C, Pettus T R R. Oxidative dearomatization of resorcinol derivatives: Useful conditions leading to valuable cyclohexa-2,5-dienones. Tetrahedron Letters. 2003, 44(27): 5109–5113

    Article  Google Scholar 

  17. Zhu J, Germain A R, Porco J A. Synthesis of azaphilones and related molecules by employing cycloisomerization of O-alkynylbenzaldehydes. Angewandte Chemie International. 2004, 43(10): 1239–1243

    Article  CAS  Google Scholar 

  18. Jia Z, Galvez E, Sebastian R M, Pleixats R, Alvarez-Larena A, Martin E, Vallribera A, Shafir A. An alternative to the classical alpha-arylation: The transfer of an intact 2-iodoaryl from ArI (O2CCF3)2. Angewandte Chemie International Edition. 2014, 53(42): 11298–11301

    Article  CAS  Google Scholar 

  19. Khatri H R, Zhu J. Synthesis of complex ortho-allyliodoarenes employing reductive iodonio-Claisen rearrangement. Chemistry (Weinheim an der Bergstrasse, Germany). 2012, 18(39): 12232–12236

    CAS  Google Scholar 

  20. Nguyen H, Khatri H R, Zhu J. Reductive iodonio-Claisen rearrangement of iodothiophene diacetates with allylsilanes: Formal synthesis of Plavix®. Tetrahedron Letters. 2013, 54(40): 5464–5466

    Article  CAS  Google Scholar 

  21. Bonnet-Delpon D, Bégué J P, Crousse B. Fluorinated alcohols: A new medium for selective and clean reaction. Synlett. 2004, (1): 18–29

    Article  Google Scholar 

  22. Dohi T, Yamaoka N, Kita Y. Fluoroalcohols: Versatile solvents in hypervalent iodine chemistry and syntheses of diaryliodonium(III) salts. Tetrahedron. 2010, 66(31): 5775–5785

    Article  CAS  Google Scholar 

  23. Kita Y, Yakura T, Tohma H, Kikuchi K, Tamura Y. A synthetic approach to discorhabdin alkaloids: Hypervalent iodine oxidation of p-substituted phenol derivatives to azacarbocyclic spirodienones. Tetrahedron Letters. 1989, 30(9): 1119–1120

    Article  CAS  Google Scholar 

  24. Kita Y, Tohma H, Kikuchi K, Inagaki M, Yakura T. Hypervalent iodine oxidation of N-acyltyramines: Synthesis of quinol ethers, spirohexadienones, and hexahydroindol-6-ones. Journal of Organic Chemistry. 1991, 56(1): 435–438

    Article  CAS  Google Scholar 

  25. Kita Y, Tohma H, Inagaki M, Hatanaka K, Kikuchi K, Yakura T. Hypervalent iodine oxidation of O-silylated phenol derivatives to azacarbocyclic spirodienones; Synthetic approach to the anticancer marine alkaloid, Discorhabdin C. Tetrahedron Letters. 1991, 32(18): 2035–2038

    Article  CAS  Google Scholar 

  26. Kita Y, Tohma H, Inagaki M, Hatanaka K, Yakura T. Total synthesis of discorhabdin C: A general aza spiro dienone formation from O-silylated phenol derivatives using a hypervalent iodine reagent. Journal of the American Chemical Society. 1992, 114(6): 2175–2180

    Article  CAS  Google Scholar 

  27. Kita Y, Arisawa M, Gyoten M, Nakajima M, Hamada R, Tohma H, Takada T. Oxidative intramolecular phenolic coupling reaction induced by a hypervalent iodine (III) reagent: Leading to galanthamine-type amaryllidaceae alkaloids. Journal of Organic Chemistry. 1998, 63(19): 6625–6633

    Article  CAS  Google Scholar 

  28. Tohma H, Harayama Y, Hashizume M, Iwata M, Kiyono Y, Egi M, Kita Y. The first total synthesis of Discorhabdin A. Journal of the American Chemical Society. 2003, 125(37): 11235–11240

    Article  CAS  Google Scholar 

  29. Kita Y, Tohma H, Hatanaka K, Takada T, Fujita S, Mitoh S, Sakurai H, Oka S. Hypervalent iodine-induced nucleophilic substitution of para-substituted phenol ethers. Generation of cation radicals as reactive intermediates. Journal of the American Chemical Society. 1994, 116(9): 3684–3691

    Article  CAS  Google Scholar 

  30. Kita Y, Takada T, Mihara S, Whelan B A, Tohma H. Novel and direct nucleophilic sulfenylation and thiocyanation of phenol ethers using a hypervalent iodine (III) reagent. Journal of Organic Chemistry. 1995, 60(22): 7144–7148

    Article  CAS  Google Scholar 

  31. Dohi T, Ito M, Morimoto K, Minamitsuji Y, Takenaga N, Kita Y. Versatile direct dehydrative approach for diaryliodonium (III) salts in fluoroalcohol media. Chemical Communications. 2007, 40(40): 4152–4154

    Article  Google Scholar 

  32. Schadt F L, Bentley T W, Schleyer P R. The SN2-SN1 spectrum. 2. Quantitative treatments of nucleophilic solvent assistance. A Scale of solvent nucleophilicities. Journal of the American Chemical Society, 1976, 98(24): 7667–7675

    Article  CAS  Google Scholar 

  33. Kuwabe S, Torraca K E, Buchwald S L. Palladium-catalyzed intramolecular C–O bond formation. Journal of the American Chemical Society. 2001, 123(49): 12202–12206

    Article  CAS  Google Scholar 

  34. Shafir A, Buchwald S L. Highly selective room-temperature coppercatalyzed C–N coupling reactions. Journal of the American Chemical Society. 2006, 128(27): 8742–8743

    Article  CAS  Google Scholar 

  35. Che C Y, Dormer P G. Synthesis of benzo [b] furans via CuIcatalyzed ring closure. Journal of Organic Chemistry. 2005, 70(17): 6964–6967

    Article  Google Scholar 

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry and School of Green Chemistry and Engineering, The University of Toledo, Toledo, OH, 43606, USA

    Hem Raj Khatri, Hai Nguyen, James K. Dunaway & Jianglong Zhu

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  1. Hem Raj Khatri
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  2. Hai Nguyen
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  3. James K. Dunaway
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  4. Jianglong Zhu
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Correspondence to Jianglong Zhu.

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Dedicated to the 120th Anniversary of Tianjin University

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Khatri, H.R., Nguyen, H., Dunaway, J.K. et al. Fluoroalcohol-mediated reductive iodonio-Claisen rearrangement: Synthesis of complex ortho-substituted-allyl iodoarenes. Front. Chem. Sci. Eng. 9, 359–368 (2015). https://doi.org/10.1007/s11705-015-1530-6

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