- Synthesis of 1,3-Diynes via Cadiot-Chodkiewicz Coupling of Volatile, in Situ Generated Bromoalkynes
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A convenient Cadiot-Chodkiewicz protocol that facilitates the use of low molecular weight alkyne coupling partners is described. The method entails an in situ elimination from a dibromoolefin precursor and immediate subjection to copper-catalyzed conditions, circumventing the hazards of volatile brominated alkynes. The scope of this method is described, and the internal 1,3-diyne products are preliminarily evaluated in ruthenium-catalyzed azide-alkyne cycloadditions.
- Knutson, Phil C.,Fredericks, Haleigh E.,Ferreira, Eric M.
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supporting information
p. 6845 - 6849
(2018/10/25)
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- A comparative study of the synthetic paths from 1-butyne to 2E,4Z-heptadien-1-ol
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2E,4Z-Heptadien-1-ol (1), the key intermediate in the synthesis of the grapevine moth sex pheromone, was obtained from 1-butyne by a number of alternative procedures, including various variants of the stereocontrolled building of the conjugated E,Z-diene system (Cadiot-Chodkiewicz cross-coupling, alkyne-vinyl halide cross-coupling catalyzed by palladium complexes, anionotropic allylic rearrangement, partial cis- and trans-reduction of the triple bond).None of them could provide for configurational uniformity of 1.The most acceptable path to obtain 1 in multigram amounts appears to be that which proceeds via the conjugated diynol and enynol intermediates with subsequent catalytic cis-hydrogenation.
- Mavrov, M. V.,Chrelashvili, Z. G.,Serebryakov, E. P.
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p. 737 - 741
(2007/10/02)
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- Synthesis of 7E,9Z-dodecadienyl acetate, the sex pheromone of Lobesia botrana Shiff
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Two syntheses of 7E,9Z-dodecadienyl acetate from 1,3-butadiyne were carried out using either 2E,4Z-heptadienyl acetate or 1-bromo-3E,5Z-octadiene as the key intermediates.The latter underwent organocopper cross-coupling with the respective complementary Grignard reagents (prepared from the corresponding 1-tert-butoxy-ω-chlorohydrins) as alkylating agents.
- Chrelashvili, Z. G.,Mavrov, M. V.,Dolidze, A. V.,Voronkov, A. P.,Serebryakov, E. P.
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p. 734 - 736
(2007/10/02)
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