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. Author manuscript; available in PMC: 2012 Jan 1.
Published in final edited form as: Chem Sci. 2011;4(2):573–589. doi: 10.1039/C0SC00394H

Table 3. Chemoselective reductive cross-coupling reactions of 1,5-dienes as a route to stereodefined skipped trienes.

graphic file with name nihms269836u3.jpg
entry alkyne 1,5-diene yield (%)a skipped triene product
1 graphic file with name nihms269836t27.jpg graphic file with name nihms269836t28.jpg 60b graphic file with name nihms269836t29.jpg
2 graphic file with name nihms269836t30.jpg graphic file with name nihms269836t31.jpg 51b graphic file with name nihms269836t32.jpg
3 graphic file with name nihms269836t33.jpg 146 54b graphic file with name nihms269836t34.jpg
4 graphic file with name nihms269836t35.jpg 146 65 graphic file with name nihms269836t36.jpg
5 graphic file with name nihms269836t37.jpg graphic file with name nihms269836t38.jpg 58b graphic file with name nihms269836t39.jpg
a

Reaction conditions: alkyne (2-3 equiv.), Ti(Oi-Pr)4 or ClTi(Oi-Pr), c-C5H9MgCl, PhMe (−78 to −35 °C), then cool to −78 °C and add Li alkoxide of the allylic alcohol as a solution in THF (warm to 0 °C).

b

Yield reported is over two steps: chemoselective reductive cross-coupling and silyl deprotection with TBAF in THF.