New Method Based on 1-(Trimethysilyl)alk-1-yne To Prepare 1,4-Skipped Diynes

Abstract

[reaction: see text] We have developed a novel reaction between a terminal TMS-alkyne and a propargyl halide in the presence of a fluoride source and a catalytic amount of copper iodide to prepare 1,4-skipped diynes with good yields and in mild conditions. We have shown that this reaction also works very well with germanium and tin derivatives as an alternative to silicon. This new method can be useful for the synthesis of polyunsaturated fatty acids.

Unified total synthesis of the natural products endiandric acid A, kingianic acid E, and kingianins A, D, and F

“…This short sequence has been reproduced several times to prepare multi-gram quantities of tetrayne 8 . 18 All attempts to directly generate an anionic-tetrayne species from TMS tetrayne 8 using TBAF 19 or MeLi 17 b led to decomposition. This problem was solved by firstly generating the terminal tetrayne 13 20 by selective desilylation of 8 with potassium carbonate in methanol, and subsequent metalation with tert -butylmagnesium bromide.…”

Some Aspects of the Chemistry of Alkynylsilanes

“…The reaction proceeded well with 1-phenyl-2-(tributylstannyl)acetylene (70%) and 4-phenyl-1-(trimethylgermyl)but-1-yne (90%) (Scheme 19). 24 Denmark and Tymonko demonstrated the cross-coupling of alkynyldimethylsilanols with aryl iodides under promotion with potassium trimethylsilanolate (Scheme 20). 25 This protocol avoids the typical necessity of fluoride ion promotion and the associated disadvantages of cost and low tolerance for silicon-based protecting groups.…”

Rhenium‐ and Gold‐Catalyzed Coupling of Aromatic Aldehydes with Trimethyl(phenylethynyl)silane: Synthesis of Diethynylmethanes

“…Recently, synthetic reactions using a combination of two metal complexes have received considerable attention because they lead to products that cannot be synthesized with only one of the catalysts 1. We report herein on the rhenium‐2, 3 and gold‐catalyzed4 synthesis of diethynylmethanes5, 6 by reactions of aldehydes with trimethyl(phenylethynyl)silane.…”