A nickel-catalyzed carbozincation of aryl-substituted alkynes

doi:10.1016/S0040-4020(97)10226-5

Tetrahedron

Volume 54, Issue 7, 12 February 1998, Pages 1299-1316

https://doi.org/10.1016/S0040-4020(97)10226-5 Get rights and content

Abstract

The addition of dialkylzincs or diphenylzinc to substituted phenylacetylenes in the presence of catalytic amounts of Ni(acac)₂ in THF : NMP mixtures produces syn-carbozincation products with good to excellent regio- and stereoselectivity. After quenching with an electrophile (iodine, acyl chloride, allyl bromide) tetrasubstituted olefines are obtained in good to satisfactory yields. An intramolecular version of the reaction is possible using a terminal triple bond bearing an iodine at a remote position. More substituted iodo-alkynes furnish only reductive elimination products. An application to a stereoselective synthesis of (Z)-tamoxifen (Z : E>99 : 1) has been developed.

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A nickel-catalyzed carbozincation of aryl-substituted alkynes

Abstract

Tetrahedron Lett.

J. Organomet. Chem.

J. Organomet. Chem.

Synth. Commun.

Synthesis

J. Chem. Soc., Perkin Trans 1

J. Org. Chem.

Synthesis

Pure Appl. Chem.

Organometallics

J. Org. Chem.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

Isr. J. Chem.

Angew. Chem.

Angew. Chem. Int. Ed. Engl.

J. Am. Chem. Soc.

J. Org. Chem.

Chem. Ber.

J. Am. Chem. Soc.

Isr. J. Chem.

J. Am. Chem. Soc.