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Synlett 2011(12): 1766-1768  
DOI: 10.1055/s-0030-1260812
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

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

Tetsuya Sengokua, Tomoya Hamamatsua, Toshiyasu Inuzukab, Masaki Takahashia, 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
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Publication History

Received 31 March 2011
Publication Date:
29 June 2011 (online)

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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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10

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

11

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

13

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

Scheme 5