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Updated: Jun 28, 2026

Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols
Published on: April 4, 2014
Iron-catalyzed enyne cross-coupling reaction.
Takuji Hatakeyama1, Yuya Yoshimoto, Toma Gabriel
1International Research Center for Elements Science, Institute for Chemical Research, Kyoto University, Uji, Kyoto, 611-0011, Japan.
This study introduces a new method for synthesizing conjugated enynes using alkynyl Grignard reagents and alkenyl electrophiles. The reaction is catalyzed by iron(III) chloride and a lithium bromide additive, achieving high yields.
Area of Science:
- Organic Chemistry
- Synthetic Chemistry
Background:
- Alkynyl Grignard reagents are versatile synthetic intermediates.
- Conjugated enynes are valuable building blocks in organic synthesis.
Purpose of the Study:
- To develop an efficient catalytic method for synthesizing conjugated enynes.
- To explore the scope and limitations of the new synthetic route.
Main Methods:
- Preparation of alkynyl Grignard reagents from terminal alkynes and methylmagnesium bromide.
- Catalytic coupling of alkynyl Grignard reagents with alkenyl bromides or triflates using FeCl(3) and LiBr.
Main Results:
- High to excellent yields of conjugated enynes were obtained.
- The reaction demonstrated broad applicability to diverse terminal alkynes and alkenyl electrophiles.
- Iron(III) chloride (FeCl(3)) and lithium bromide (LiBr) were effective catalysts and additives.
Conclusions:
- A novel and efficient synthesis of conjugated enynes has been established.
- The described methodology offers a practical approach for accessing valuable enyne structures.
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