New Synthetic Methodology toward
Macrolides/Macrolactams via Palladium-Catalyzed Carbon-Heteroatom
Bond-Forming Reactions

Tetsuya Sengoku; Tomoya Hamamatsu; Toshiyasu Inuzuka; Masaki Takahashi; Hidemi Yoda

doi:10.1055/s-0030-1260812

LETTER

New Synthetic Methodology toward Macrolides/Macrolactams via Palladium-Catalyzed Carbon-Heteroatom Bond-Forming Reactions

Tetsuya Sengoku^a, Tomoya Hamamatsu^a, Toshiyasu Inuzuka^b, Masaki Takahashi^a, Hidemi Yoda*^a
^a Department of Materials Science, Faculty of Engineering, Shizuoka University, 3-5-1 Johoku, Naka-ku, Hamamatsu, Shizuoka 432-8561, Japan
Fax: +81(53)4781150; e-Mail: tchyoda@ipc.shizuoka.ac.jp;
^b Division of Instrumental Analysis, Life Science Research Center, Gifu University, 1-1 Yanagido, Gifu 501-1193, Japan

Abstract

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Abstract

A concise and versatile syntheses of 11-16-membered macrolides and 13-15-membered macrolactams have been achieved using a Tsuji-Trost type reaction. This approach is composed of intramolecular cyclization employing ethyl carbonate with carboxylic acids and catalytic amount of Pd(PPh₃)₄ to form carbon-heteroatom covalent bonds with no use of stoichiometric reagents.

Key words

macrolactones - macrolactams - palladium-catalyzed reaction - carbon-heteroatom bond formation

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References and Notes

<A NAME="RU03111ST-1A">1a</A> Vester B. Douthwaite S. Antimicrob. Agents Chemother. 2001, 45: 1

<A NAME="RU03111ST-1B">1b</A> Schlunzen F. Zarivach R. Harms J. Bashan A. Tocilj A. Albrecht R. Yonath A. Franceschi F. Nature (London) 2001, 413: 814

<A NAME="RU03111ST-1C">1c</A> Hansen JL. Ippolito JA. Ban N. Nissen P. Moore PB. Steitz TA. Mol. Cells 2002, 10: 117

<A NAME="RU03111ST-2A">2a</A> Gerth K. Bedorf N. Hofle G. Irschik H. Reichenbach H. J. Antibiot. 1996, 49: 560

<A NAME="RU03111ST-2B">2b</A> Hofle G. Bedorf N. Steinmetz H. Schomburg D. Gerth K. Reichenbach H. Angew. Chem., Int. Ed. Engl. 1996, 35: 1567 ; Angew. Chem. 1996, 108, 1671

For recent reviews, see:

<A NAME="RU03111ST-3A">3a</A> Parenty A. Moreau X. Campagne J.-M. Chem. Rev. 2006, 106: 911

<A NAME="RU03111ST-3B">3b</A> Yeung K.-S. Paterson I. Chem. Rev. 2005, 105: 4237

<A NAME="RU03111ST-4A">4a</A> Corey EJ. Nicolaou KC. J. Am. Chem. Soc. 1974, 96: 5614

<A NAME="RU03111ST-4B">4b</A> Corey EJ. Nicolaou KC. Melvin LS. J. Am. Chem. Soc. 1975, 97: 653

<A NAME="RU03111ST-5">5</A> Inanaga J. Hirata K. Saeki H. Katsuki T. Yamaguchi M. Bull. Chem. Soc. Jpn. 1979, 52: 1989

<A NAME="RU03111ST-6A">6a</A> Shiina I. Ibuka R. Kubota M. Chem. Lett. 2002, 31: 286

<A NAME="RU03111ST-6B">6b</A> Shiina I. Kubota M. Ibuka R. Tetrahedron Lett. 2002, 43: 7535

<A NAME="RU03111ST-7A">7a</A> Fraunhoffer KJ. Prabagaran N. Sirois LE. White MC. J. Am. Chem. Soc. 2006, 128: 9032

<A NAME="RU03111ST-7B">7b</A> Stang EM. White MC. Nat. Chem. 2009, 1: 547

<A NAME="RU03111ST-8">8</A> Trost BM. Angew. Chem., Int. Ed. Engl. 1989, 28: 1173

<A NAME="RU03111ST-9A">9a</A> Liu L. Floreancig PE. Org. Lett. 2009, 11: 3152

<A NAME="RU03111ST-9B">9b</A> Kim S. Adiyaman Y. Saha G. Powell WS. Rokach J. Tetrahedron Lett. 2001, 42: 4445

<A NAME="RU03111ST-9C">9c</A> Nagano H. Tada A. Isobe Y. Yajima T. Synlett 2000, 1193

<A NAME="RU03111ST-9D">9d</A> Makado G. Morimoto T. Sugimoto Y. Tsutsumi K. Kagawa N. Kakiuchi K. Adv. Synth. Catal. 2010, 352: 299

<A NAME="RU03111ST-9E">9e</A> He W. Soll CE. Chavadi SS. Quadri LEN. J. Am. Chem. Soc. 2009, 131: 16744

We observed that the reaction with the isolated single (E)-α-7c under the same reaction conditions afforded a 90:10 mixture of E/Z-isomers without production of γ-7c (Scheme [4] ).

Scheme 4

This would be attributed to the strain based on the ring size.

<A NAME="RU03111ST-12">12</A> Leonard NJ. Cruickshank KA. J. Org. Chem. 1985, 50: 2480

The macrolactamization of 9c in the absence of KOt-Bu resulted in α-12c in 44% yield (Scheme [5] ).

Scheme 5

Supplementary Material

Supporting Information