Enantioselective Alkenylation via Nickel-Catalyzed Cross-Coupling with Organozirconium Reagents

Sha Lou; Guofeng Fu

doi:10.1021/ja1017046

journal article Mar 19, 2010

Enantioselective Alkenylation via Nickel-Catalyzed Cross-Coupling with Organozirconium Reagents

Sha Lou Guofeng Fu

Journal of the American Chemical Society Vol. 132 No. 14 pp. 5010-5011 · American Chemical Society (ACS)

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References

34

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Notes:

[29]

aIn the absence of NiCl2•glyme or ligand1, the desired product is generated in <5% yield. NiBr2•glyme or Ni(cod)2may be used in place of NiCl2•glyme.

[30]

bFor the cross-coupling illustrated in entry 3 of Table1: a reaction on a gram scale proceeded at room temperature in 90% yield and 92% ee; use of 1.1, rather than 2, equiv of the organozirconium reagent led to a slower reaction (after 3 days at room temperature: 85% yield, 91% ee).

[31]

cDuring the cross-coupling, no kinetic resolution of the starting material (the racemic secondary alkyl bromide) is detected, and the ee of the product is constant.

[32]

dAfter a competition experiment with an α-bromoketone, an unactivated secondary alkyl bromide was recovered in essentially quantitative yield.

[33]

eIn preliminary studies under our standard conditions, an α-chloroketone, a cyclic α-bromoketone, and an alkenylzirconium reagent derived from hydrozirconation of an internal alkyne were not suitable cross-coupling partners.

[34]

fThe rate law for the cross-coupling is first-order in the catalyst and in the nucleophile, and it is zero-order in the electrophile (NMR studies ind8-THF).

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Details

Published: Mar 19, 2010
Vol/Issue: 132(14)
Pages: 5010-5011

Authors

S

Sha Lou

Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139

G

Guofeng Fu

Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139

Cite This Article

Sha Lou, Guofeng Fu (2010). Enantioselective Alkenylation via Nickel-Catalyzed Cross-Coupling with Organozirconium Reagents. Journal of the American Chemical Society, 132(14), 5010-5011. https://doi.org/10.1021/ja1017046

Enantioselective Alkenylation via Nickel-Catalyzed Cross-Coupling with Organozirconium Reagents

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