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Synthesis 2008(22): 3591-3600  
DOI: 10.1055/s-0028-1083201
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

One-Pot Synthesis of Internal Conjugated (Z)-Enynyltrimethylsilanes Possessing Aryl, Cycloalkenyl, (E)- or (Z)-Alk-1-enyl Moieties on the sp Carbon Atom via Two Types of Cross-Coupling Reaction

Masayuki Hoshi*, Tomohiko Iizawa, Mitsuhiro Okimoto, Kazuya Shirakawa
Department of Biotechnology and Environmental Chemistry, Kitami Institute of Technology, 165 Koen-cho, Kitami, Hokkaido 090-8507, Japan
Fax: +81(157)247719; e-Mail: hoshi-m@chem.kitami-it.ac.jp;
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Publication History

Received 14 July 2008
Publication Date:
23 October 2008 (online)

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Abstract

Described herein is an operationally simple and mild method for the stereospecific synthesis of internal conjugated (Z)-enynyltrimethylsilanes whose conjugation is extended away from the distal alkynyl carbon atom. This protocol involves two types of cross-coupling reaction, a Suzuki-type reaction and a sila-Sonogashira reaction, and the desired synthesis can be performed in a one-pot manner. Thus, the copper-mediated cross-coupling reaction of dicyclohexyl[(Z)-1-(trimethylsilyl)alk-1-enyl]boranes with (trimethylsilyl)ethynyl bromide is carried out in the presence of aqueous lithium hydroxide at -15 ˚C to room temperature, resulting in the stereospecific formation of (Z)-1,3-bis(trimethylsilyl)alk-3-en-1-ynes. Subsequent reaction is allowed to proceed without isolation of the enynes. Thus, palladium/copper-catalyzed cross-coupling reactions with aryl iodides, cycloalk-1-enyl triflates, and (E)- and (Z)-alk-1-enyl iodides can be accomplished in the presence of either 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or tetrabutylammonium fluoride (TBAF) at ambient temperature to provide the corresponding internal conjugated (Z)-enynyltrimethylsilanes possessing one more sp-sp² carbon bond.

Key words

(Z)-enynyltrimethylsilane - (trimethylsilyl)ethynyl bromide - (Z)-1,3-bis(trimethylsilyl)alk-3-en-1-yne - Suzuki-type reaction - sila-Sonogashira reaction

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10

Compound 2a was formed in about 90% GC yield based on Me3SiC≡CBr employed; see ref. 6.

11

Addition of CuI was not necessary because CuI had already been used for the cross-coupling reaction of 1a with Me3SiC≡CBr.

14

Compound 2a was formed in 82% (0.375 mL of H2O) or 84% GC yield (0.75 mL of H2O), based on Me3SiC≡CBr employed.

22

After column chromatography, the product in eluates should be stored in the refrigerator to avoid decomposition.