Synthesis of the C1-C15 Fragment of Apicularen A through a Regioselective Electron-Transfer-Initiated Cyclization Reaction

Alexander J. Poniatowski; Paul E. Floreancig

doi:10.1055/s-2007-983776

PAPER

Synthesis of the C₁-C₁₅ Fragment of Apicularen A through a Regioselective Electron-Transfer-Initiated Cyclization Reaction

Alexander J. Poniatowski, Paul E. Floreancig*
Department of Chemistry, University of Pittsburgh, Pittsburgh, PA 15260, USA
e-Mail: florean@pitt.edu;

Abstract

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Abstract

In this paper we report the preparation of the benzyltetrahydropyran fragment of the vacuolar ATPase inhibitor apicularen A through an oxidative cyclization protocol. In this reaction regioselective cleavage of one homobenzylic ether in the presence of another homobenzylic ether is achieved by selectively weakening one carbon-carbon σ-bond through substitution. This work demonstrates that oxidative fragmentation reactions can be used to generate stable cations selectively, even in the presence of other readily oxidized groups, provided that bond cleavage is sufficiently rapid following oxidation.

Key words

acetals - cations - cyclizations - electron transfer - oxidations

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References

<A NAME="RC01307SS-1A">1a</A> Kumar VS. Floreancig PE. J. Am. Chem. Soc. 2001, 123: 3842

<A NAME="RC01307SS-1B">1b</A> Aubele DL. Floreancig PE. Org. Lett. 2002, 4: 3443

<A NAME="RC01307SS-1C">1c</A> Floreancig PE. Synlett 2007, 191

<A NAME="RC01307SS-2">2</A> Rech JC. Floreancig PE. Org. Lett. 2003, 5: 1495

<A NAME="RC01307SS-3">3</A> Kumar VS. Aubele DL. Floreancig PE. Org. Lett. 2002, 4: 2489

<A NAME="RC01307SS-4A">4a</A> Kunze B. Jansen R. Sasse F. Höfle G. Reichenbach H. J. Antibiot. 1998, 51: 1075

<A NAME="RC01307SS-4B">4b</A> Jansen R. Kunze B. Reichenbach H. Höfle G. Eur. J. Org. Chem. 2000, 913

<A NAME="RC01307SS-5">5</A> Erickson KL. Beutler JA. Cardellina JH. Boyd MR. J. Org. Chem. 1997, 62: 8188

<A NAME="RC01307SS-6">6</A> McKee TC. Galinis DL. Pannell LK. Cardellina JH. Laakso J. Ireland CM. Murray L. Capon RJ. Boyd MR. J. Org. Chem. 1998, 63: 7805

<A NAME="RC01307SS-7">7</A> Kim JW. Shin-ya K. Furihata K. Hayakawa Y. Seto H. J. Org. Chem. 1999, 64: 153

<A NAME="RC01307SS-8">8</A> Hong JJ. Yokomakura A. Nakano Y. Ishihara K. Kaneda M. Onodera M. Nakahama K. Morita I. Niikura K. Ahn J.-W. Zee O. Ohuchi K. FEBS Lett. 2006, 580: 2723

<A NAME="RC01307SS-9">9</A> Keeling DJ. Herslof M. Ryberg B. Sjogren S. Solvell L. Ann. N. Y. Acad. Sci. 1997, 834: 600

<A NAME="RC01307SS-10A">10a</A> Blair HC. Teitelbaum SL. Ghiselli R. Gluck S. Science (Washington, D.C.) 1989, 245: 855

<A NAME="RC01307SS-10B">10b</A> Farina C. Gagliardi S. Drug Discovery Today 1999, 4: 163

<A NAME="RC01307SS-11A">11a</A> Bhattacharjee A. Seguil OR. De Brabander JK. Tetrahedron Lett. 2001, 42: 1217

<A NAME="RC01307SS-11B">11b</A> Nicolaou KC. Kim DW. Baati R. O’Brate A. Giannakakou P. Chem. Eur. J. 2003, 9: 6177

<A NAME="RC01307SS-11C">11c</A> Su Q. Panek JS. J. Am. Chem. Soc. 2004, 126: 2425

<A NAME="RC01307SS-11D">11d</A> Petri AF. Bayer A. Maier ME. Angew. Chem. Int. Ed. 2004, 43: 5821

<A NAME="RC01307SS-12A">12a</A> Lewis A. Stefanuti I. Swain SA. Smith SA. Taylor RJK. Org. Biomol. Chem. 2003, 1: 104

<A NAME="RC01307SS-12B">12b</A> Graetz BR. Rychnovsky SD. Org. Lett. 2003, 5: 3357

<A NAME="RC01307SS-12C">12c</A> Hilli F. White JM. Rizzacasa MA. Org. Lett. 2004, 6: 1289

<A NAME="RC01307SS-12D">12d</A> Li M. O’Doherty GA. Org. Lett. 2006, 8: 6087

<A NAME="RC01307SS-13">13</A> Blanksby SJ. Ellison GB. Acc. Chem. Res. 2003, 36: 255

<A NAME="RC01307SS-14A">14a</A> Seiders JR. Wang L. Floreancig PE. J. Am. Chem. Soc. 2003, 125: 2406

<A NAME="RC01307SS-14B">14b</A> Wang L. Seiders JR. Floreancig PE. J. Am. Chem. Soc. 2004, 126: 12596

<A NAME="RC01307SS-15">15</A> Kozikowski AP. Floyd WC. Kuniak MP. J. Chem. Soc., Chem. Commun. 1977, 582

<A NAME="RC01307SS-16">16</A> Wiley RH. Jarboe CH. J. Am. Chem. Soc. 1956, 78: 2398

<A NAME="RC01307SS-17">17</A> Node M. Fujiwara T. Ichihashi S. Nishide K. Tetrahedron Lett. 1998, 39: 6331

<A NAME="RC01307SS-18">18</A> Rech JC. Floreancig PE. Org. Lett. 2005, 7: 5175

<A NAME="RC01307SS-19">19</A> Caron S. Vazquez E. Wojcik JM. J. Am. Chem. Soc. 2000, 122: 712

<A NAME="RC01307SS-20">20</A> Denmark SE. Fu J. Chem. Rev. 2003, 103: 2763

<A NAME="RC01307SS-21">21</A> Noyori R. Murata S. Suzuki M. Tetrahedron 1981, 37: 3899

<A NAME="RC01307SS-22A">22a</A> Overman LE. Pennington LD. J. Org. Chem. 2003, 68: 7143

<A NAME="RC01307SS-22B">22b</A> Aubele DL. Wan S. Floreancig PE. Angew. Chem. Int. Ed. 2005, 44: 3485

<A NAME="RC01307SS-23A">23a</A> Bartlett PA. Johnson WS. Elliott JD. J. Am. Chem. Soc. 1983, 105: 2088

<A NAME="RC01307SS-23B">23b</A> Denmark SE. Willson TM. Almstead NG. J. Am. Chem. Soc. 1989, 111: 9258

<A NAME="RC01307SS-23C">23c</A> Denmark SE. Almstead NG. J. Am. Chem. Soc. 1991, 113: 8089

<A NAME="RC01307SS-23D">23d</A> Denmark SE. Almstead NG. J. Org. Chem. 1991, 56: 6458

<A NAME="RC01307SS-23E">23e</A> Denmark SE. Almstead NG. J. Org. Chem. 1991, 56: 6485

<A NAME="RC01307SS-23F">23f</A> Sammakia T. Smith RS. J. Am. Chem. Soc. 1992, 114: 10998

<A NAME="RC01307SS-24">24</A> Myers AG. Zheng B. J. Am. Chem. Soc. 1996, 118: 4492

<A NAME="RC01307SS-25A">25a</A> Goossen LJ. Paetzold J. Koley D. Chem. Commun. 2003, 706

<A NAME="RC01307SS-25B">25b</A> Neveux M. Bruneau C. Dixneuf PH. J. Chem. Soc., Perkin Trans. 1 1991, 1197

<A NAME="RC01307SS-26">26</A> For another illustrative example, see: Duan S. Moeller KD. J. Am. Chem. Soc. 2002, 124: 9368