Science of Synthesis

Negishi, E.-i.; Takahashi, T., Science of Synthesis, (2003) 2, 707.

The reaction of alkyl halides with a bis(η5-cyclopentadienyl)zirconium derivative “Zr(Cp)2” has been shown to give products of the type [Zr(Cp)2R1X].[‌127‌] Primary alkyl halides generally give such complexes in good yields, whereas tertiary alkyl halides predominantly or exclusively produce compounds of the type [Zr(Cp)2X2]. With secondary alkyl halides, mixtures of the two kinds of product are obtained.[‌127‌] The reaction has been shown to proceed via radical intermediates. The reaction of allylic and propargylic ethers with dibutylbis(η5-cyclopentadienyl)zirconium(IV) (‌64‌) and similar derivatives as “Zr(Cp)2” equivalents provides a convenient route to monoallyl- and monoallenylbis(η5-cyclopentadienyl)zirconium derivatives such as ‌65‌-‌69‌ (‌Scheme 28‌).[‌13‌,‌97‌,‌128‌,‌129‌]

‌Meeeee 88‌ Meeeeeeee ee Meeee- eee Meeeeeeeee(η8-eeeeeeeeeeeeeeee)eeeeeeeee Meeeeeeeeee ee Meeeeeeee Meeeeeee[‌88‌,‌888‌,‌888‌]

Mee eeeee ee eeeeeeeee eeeeeeee ee e eeeee ee [Me(Me)8M8M] eeeeeeeee eee eeee eeeeeeeeeeeee eeeeeeee ee eee eeeeeeeeee eee ee 8-eeeeeeeee-8-eeee ee eeeeeee eeeeee “Meeeeeeeeee” eeeeeeeeeeeeeeee eeeeeeee ‌88‌ (‌Meeeee 88‌).[‌888‌] Me eeeee eeeeeeeee eee eeeeeeeee ee eeeeeee eeeeee eee eeeeeeeeeeeee ee eeee eeeeee ee eee eeeeeeeee ee eee(η8-eeeeeeeeeeeeeeee)eeeeeeeeeeeeeeeeeee eeeeeeeee eeeeeeeeee eeee, eeeeeee, eeeeee, eeeeeeeee, eee eeeee eeeeee-eeeeeeeeee eeeeee.

‌Meeeee 88‌ Meeeeeeee Meeeeeee ee 8-Meeeeeeee-8-eeee ee Mee(η8-eeeeeeeeeeeeeeee)eeeeeeeee Meeeeeeeeee[‌888‌]

Meeeeeeeeeee Meeeeeeee

Meeeeeeee(η8-eeeeeeeeeeeeeeee)(eeeeeeeeeee)eeeeeeeee(MM) (‌88‌, M8 = Me); Meeeeee Meeeeeeee:[‌888‌]

Me eeee eeeeeeeeeee: M 8.8 M eeee ee MeMe ee eeeeee (8.88 ee, 8 eeee) eee eeeee ee e eeee ee [Me(Me)8Me8] (‌88‌; 888 ee, 8 eeee) ee MMM (8 eM) ee −88°M eee eee eeeeeee eee eeeeeee eee 8 e. Meeee eeeeeeee eee eeeeeee eeee, 8-eeeeeeeeeeeee (88 ee, 8 eeee) eee eeeee eee eeeeeeee eee eeeeeeeee eee e eeeeeee 8 e. Mee eeeeeeee eeeeee eee eeeeeee eeeeeee ‌88‌ (M8 = Me) eee eeeee ee ee 88% eeeeeeee ee MMM eeeeeeeeeeee.

Meeeeeeee: M 8.8 M eeee ee MeMeMe ee Me8M (8.8 eM, 8.8 eeee) eee eeeee ee e eeeeeeeeee ee [Me(Me)8Me8] (‌88‌; 888 ee, 8.8 eeee) ee Me8M (88 eM) ee −88°M. Mee eeeeeee eeeeee eeeeee. Meeee eeeeeeee eee 8 e ee −88°M, 8-eeeeeeeeeeeee (8.88 eM, 8.8 eeee) eee 8,8-eeeeeee (888 μM) eeee eeeee eee eeeeeeee eee eeeeeeeee eee 8 e ee ee. Mee eeeeeeeeeeee eeeeeeeee eeeee eeee eeeeeee ee eeeeeeeeee, eee eee eeeeeee eee eeeeeee eeee eee eeeee eeeeeeee ee eeeee. Mee eeeeeee eee eeeeeeeeeeeeee (Me8M) ee eeee eee eeeeeee ‌88‌ (M8 = Me); eeeee: 8.88 e (88%); 8M MMM (eeeeeee-e8, δ): 8.88 (ee, M = 8.8 Me, 8M), 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (e, 88M); 88M MMM (eeeeeee-e8, δ): 88.8, 888.8, 888.8, 888.8.

References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) M 88e8, 888.