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DOI: 10.1055/s-2007-990906
Oxidative Amidation of Phenols through the Use of Hypervalent Iodine Reagents: Development and Applications
Publikationsverlauf
Publikationsdatum:
15. November 2007 (online)
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Abstract
This contribution reviews a family of reactions devised in our laboratory that effect the oxidative conversion of phenols into 4-amido-dienones. A salient feature of this chemistry is the use of hypervalent iodine reagents, especially diacetoxyiodobenzene (DIB), as uniquely capable oxidants in the context of the new transformation. The advent of this methodology has created new opportunities in alkaloid synthesis. Our efforts toward FR-901483, TAN-1251C, cylindricine C, and other nitrogenous natural products illustrate some applications in that domain.
1 Introduction
2 Background
3 First-Generation Oxidative Amidation of Phenols: The Oxazoline Route
4 Initial Applications: Total Synthesis of FR-901483 and of TAN-1251C
5 Second-Generation Oxidative Amidation of Phenols: Sulfonamide Technology
6 Applications: Total Synthesis of (-)-Cylindricine C
7 Third-Generation Solution: The Bimolecular Reaction
8 Conclusion
Key words
phenols - amides - oxidation - hypervalent iodine - alkaloids
- 1
Sakamoto K.Tsujii E.Abe F.Nakanishi T.Yamashita M.Shigematsu N.Izumi S.Okuhara M. J. Antibiot. 1996, 49: 37 - 2
Shirafuji H,Tsubotani S,Ishimaru T, andHarada S. inventors; Int. Patent PCT WO91/13887. - For alternative avenues to these substances, see:
-
3a
Snider BB.Lin H. J. Am. Chem. Soc. 1999, 121: 7778 -
3b
Snider BB.Lin H. Org. Lett. 2000, 2: 643 -
3c
Maeng J.-H.Funk RL. Org. Lett. 2001, 3: 1125 -
3d
Kan T.Fujimoto T.Ieda S.Asoh Y.Kitaoka H.Fukuyama T. Org. Lett. 2004, 6: 2729 -
3e
Brummond KM.Hong S. J. Org. Chem. 2005, 70: 907 -
3f For synthetic studies see:
Simila STM.Martin SF. J. Org. Chem. 2007, 72: 5342 ; and references cited therein - 4
Kikugawa Y.Kawase M. J. Am. Chem. Soc. 1984, 106: 5728 -
5a
Glover SA.Goosen A.McCleland CW.Schoonraad JL. J. Chem. Soc., Perkin Trans. 1 1984, 2255 -
5b
Glover SA.Scott AP. Tetrahedron 1989, 45: 1763 - 6
Kawase M.Kitamura T.Kikugawa Y. J. Org. Chem. 1989, 54: 3394 - Reviews:
-
7a
Moriarty RM. J. Org. Chem. 2005, 70: 2893 -
7b
Wirth T. Angew. Chem. Int. Ed. 2005, 44: 3656 -
7c
Hamamoto H.Anilkumar G.Tohma H.Kita Y. Chem. Eur. J. 2002, 8: 5377 -
7d
Zhdankin VV.Stang PJ. Chem. Rev. 2002, 102: 2523 -
7e
Moriarty RM. Org. React. (N.Y.) 2001, 57: 327 -
7f
Varvogolis A. Hypervalent Iodine in Organic Synthesis Academic Press; San Diego CA: 1997. -
7g
Zhdankin VV.Stang PJ. Chem. Rev. 1996, 96: 1123 -
8a
Kikugawa Y.Kawase M. Chem. Lett. 1990, 581 -
8b
Kikugawa Y.Shimada M.Matsumoto K. Heterocycles 1994, 37: 293 -
9a
Wardrop DJ.Burge MS. J. Org. Chem. 2005, 70: 10271 -
9b
Wardrop DJ.Zhang W.Landrie CL. Tetrahedron Lett. 2004, 45: 4229 -
9c
Wardrop DJ.Burge MS. Chem. Commun. 2004, 1230 -
9d
Wardrop DJ.Landrie CL.Ortiz JA. Synlett 2003, 1352 -
9e
Wardrop DJ.Burge MS.Zhang W.Ortiz JA. Tetrahedron Lett. 2003, 44: 2587 -
9f
Wardrop DJ.Zhang W. Org. Lett. 2001, 3: 2353 -
9g
Wardrop DJ.Basak A. Org. Lett. 2001, 3: 1053 -
10a
Clemente D.-T.Lobo AM.Prabhakar S.Marcelo-Curto MJ. Tetrahedron Lett. 1994, 35: 2043 -
10b Review:
Prata JV.Clemente D.-TS.Prabhakar S.Lobo AM.Mourato I.Branco PS. J. Chem. Soc., Perkin Trans. 1 2002, 513 - 11
Kikugawa Y.Nagashima A.Sakamoto T.Miyazawa E.Shiiya M. J. Org. Chem. 2003, 68: 6739 - 12 See, for example:
Yamamura S. Chemistry of Phenols Vol. 2:Rappoport Z. John Wiley & Sons; Chichester: 2003. p.1153-1346 - In particular:
-
13a Usnic acid:
Barton DHR.Deflorin AM.Edwards OE. J. Chem. Soc. 1956, 530 -
13b Galanthamine:
Barton DHR.Kirby GW. J. Chem. Soc. 1962, 806 -
13c For a review, see:
Barton DHR. Pure Appl. Chem. 1964, 9: 35 - Significant contributions by other groups:
-
14a
Kametani T.Fukumoto K. Yakugaku Kenkyu 1963, 35: 426 -
14b
Scott AI.McCapra F.Buchanan RL.Day AC.Young DW. Tetrahedron 1965, 21: 3605 - 15 An excellent survey of the various oxidizing agents that have been employed for the activation of phenols is provided in:
Rodríguez S.Wipf P. Synthesis 2004, 2767 -
16a
Tamura Y.Yakura T.Haruta J.Kita Y. J. Org. Chem. 1987, 52: 3927 -
16b
Kita Y.Tohma H.Kikuchi K.Inagaki M.Yakura T. J. Org. Chem. 1991, 56: 435 - 17
Pelter A.Elgendy S. Tetrahedron Lett. 1988, 29: 677 - 18
Barret R.Daundon M. Tetrahedron Lett. 1991, 32: 2133 - 19 Review:
Kita Y.Fujioka H. Pure Appl. Chem. 2007, 79: 701 - 20
Wipf P.Spencer SR. J. Am. Chem. Soc. 2005, 127: 225 - 21
Wipf P.Jung J.-K. Chem. Rev. 1999, 99: 1469 -
22a
Knapp S.Gibson FS. Org. Synth. 1992, 70: 101 -
22b
Knapp S. In Advances in Heterocyclic Natural Product Synthesis Vol. 3:Pearson WH. JAP Press; Greenwich CT: 1996. Chap. 2. - Imidates and congeners react at the nitrogen atom with a variety of electrophiles:
- 23a Tennant G.; In Comprehensive Organic Chemistry; Barton D. H. R., Ollis W. D.; Pergamon Press: Oxford, 1979; Vol. 2: Chap. 8, 385-590; see especially page 490 onwards
-
23b
Kantlehner W. In Comprehensive Organic Synthesis Vol. 6:Trost BM. Pergamon Press; Oxford: 1991. Chap. 2.7. p.pp 485-599 ; see especially page 529 onwards -
24a
Vorbrüggen H.Krolikiewicz K. Tetrahedron Lett. 1981, 22: 4471 -
24b
Vorbrüggen H.Krolikiewicz K. Tetrahedron 1993, 49: 9353 - 25 O-Protection of the phenol, by contrast, was essential during assembly of the oxazoline by alternative techniques, such as the Wipf synthesis:
Wipf P.Miller CP. Tetrahedron Lett. 1992, 33: 907 - 26 This stereochemical assignment rests upon X-ray crystallography:
Peters K.Peters E.-M.Braun NA.Ciufolini MA. Z. Kristallogr. NCS 1999, 214: 555 - See:
-
27a
Chow YL.Colón CJ.Tan JNS. Can. J. Chem. 1968, 46: 2821 -
27b
Lunazzi L.Cerioni G.Foresti E.Macciantelli D. J. Chem. Soc., Perkin Trans. 2 1980, 717 -
27c
Johnson F. Chem. Rev. 1968, 68: 375 - 28
Braun NA.Ciufolini MA.Peters K.Peters E.-M. Tetrahedron Lett. 1998, 39: 4667 - Similar reactions in which a carbonyl group intercepts the electrophilic agent produced upon activation of the phenol are know and are synthetically useful:
-
29a
Wong Y.-S. Chem. Commun. 2002, 686 -
29b
Peuchmaur M.Wong Y.-S. J. Org. Chem. 2007, 72: 5374 - 30
Braun NA.Ousmer M.Bray JD.Bouchu D.Peters K.Peters E.-M.Ciufolini MA. J. Org. Chem. 2000, 65: 4397 - 31
Dohi T.Morimoto K.Maruyama A.Kita Y. Org. Lett. 2006, 8: 2007 - 32
Hata K.Hamamoto H.Shiozaki Y.Kita Y. Chem. Commun. 2005, 2465 - 33
Scheffler G.Seike H.Sorensen EJ. Angew. Chem. Int. Ed. 2000, 39: 4593 - 34
Mizutani H.Takayama J.Soeda Y.Honda T. Tetrahedron Lett. 2002, 43: 2411 - 36 Compare with:
Aubart KM.Heathcock CH. J. Org. Chem. 1999, 64: 16 - 38 Review:
Tsuda Y.Sano T. The Alkaloids Vol. 48:Brossi A.Cordell GA. Academic Press; Orlando: 1996. p.249 - 39
Dong Q.Anderson CE.Ciufolini MA. Tetrahedron Lett. 1995, 36: 5681 - 40
Ousmer M.Braun NA.Bavoux C.Perrin M.Ciufolini MA. J. Am. Chem. Soc. 2001, 123: 7534 - Two excellent reviews on cylindricines and related compounds have recently appeared:
-
41a
Dake G. Tetrahedron 2006, 62: 3467 -
41b
Weinreb SM. Chem. Rev. 2006, 106: 2531 - 42 See:
Ciufolini MA.Hermann CYW.Dong Q.Shimizu T.Swaminathan S.Xi N. Synlett 1998, 105 - 43 Review:
Kan T.Fukuyama T. Chem. Commun. 2004, 353 -
44a
Canesi S.Belmont P.Bouchu D.Rousset L.Ciufolini MA. Tetrahedron Lett. 2002, 43: 5193 -
44b
Canesi S.Bouchu D.Ciufolini MA. Angew. Chem. Int. Ed. 2004, 43: 4336 - 45
Drutu I.Njardson J.Wood J. Org. Lett. 2002, 4: 493 -
46a
Hutchins RO.Su WY.Sivakumar R.Cistone F.Stercho YP. J. Org. Chem. 1983, 48: 3412 -
46b
Stevens RV. Acc. Chem. Res. 1984, 17: 289 - 47
Evans DA.Gauchet-Prunet JA.Carreira EM.Charette AB. J. Org. Chem. 1991, 56: 741 ; and references cited therein - Reviews:
-
48a
Gribble GW. Org. Process Res. Dev. 2006, 10: 1062 -
48b
Abdel-Magid AF.Mehrman SJ. Org. Process Res. Dev. 2006, 10: 971 -
48c
Gribble GW. Chem. Soc. Rev. 1998, 27: 395 - 49
Kita Y.Takada T.Gyoten M.Tohma H.Zenk MH.Eichhorn J. J. Org. Chem. 1996, 61: 5857 - 50
Canesi S.Bouchu D.Ciufolini MA. Org. Lett. 2005, 7: 175 - 51 Under these conditions, products arising from capture of the electrophilic intermediate by the azido functionality were not detected; compare with:
Kita Y.Egi M.Okajima A.Ohtsubo M.Takada T.Tohma H. Chem. Commun. 1996, 1491 - 53 Review:
Livinghouse T. Tetrahedron 1999, 55: 9947 - 54 Review:
Sinclair A.Stockman RA. Nat. Prod. Rep. 2007, 24: 298 - In addition to refs. 7, 12, 22, 23, and 40, see:
-
55a
Kita Y.Takada T.Gyoten M.Tohma H.Zenk MH.Eichhorn J. J. Org. Chem. 1996, 61: 5854 -
55b
Kita Y.Gyoten M.Ohtsubo M.Tohma H.Takada T. Chem. Commun. 1996, 1481 -
55c
Takada T.Arisawa M.Gyoten M.Hamada R.Tohma H.Kita Y. J. Org. Chem. 1998, 63: 7698 -
55d
Arisawa M.Utsumi S.Nakajima M.Ramesh NG.Tohma H.Kita Y. Chem. Commun. 1999, 469 -
55e
Tohma H.Morioka H.Takizawa S.Arisawa M.Kita Y. Tetrahedron 2001, 345 -
55f
Tohma H.Iwata M.Maegawa T.Kita Y. Tetrahedron Lett. 2002, 43: 9241 -
55g
Dohi T.Morimoto K.Kiyono Y.Maruyama A.Tohma H.Kita Y. Chem. Commun. 2005, 2930 - 56
Dohi T.Maruyama A.Minamitsuji Y.Takenaga N.Kita Y. Chem. Commun. 2007, 1224 - 57
Jean A.Cantat J.Berard D.Bouchu D.Canesi S. Org. Lett. 2007, 9: 2553
References
Canesi, S. unpublished work from these laboratories.
37Schülé, A. unpublished work from these laboratories.
52Mendelsohn, B.; Ciufolini, M. A. unpublished work.