Science of Synthesis

Negishi, E.-i.; Takahashi, T., Science of Synthesis, (2003) 2, 741.

Alkene and alkyne π-complexes of zirconocene and hafnocene react with alkenes, alkynes, and other π-compounds to undergo carbometalative ring expansion leading to the formation of five-membered zirconacycles and hafnacycles (‌Scheme 76‌).

‌Meeeee 88‌ Meeeeee Meeeee eee Meeeeeeeeeeeeee Meee Meeeeeeee ee Meeee-Meeeeeee ­Meeeeeeeeee eee Meeeeeeee Meeeeeeeeee

Meee eeeeeeeeee eeeeeeeee eeeeeeeeeee ee eee eeeeeeeeeeeee eee eeeeeeeeeee. Mee eeeee eeee eeeeeeeee eeeeeeeeee-eeeeeeeeee π-eeeee eee M=M, M=M, eee M≡M eee eee eeeeeeeee ee eeee π-eeeeeeeee eee ee eeeeeeeeeeee eee eeeee eeeeeeee eeee eeee-eeeeeeee eeeeeeeeeeeee eeeeeeeeee eeeeeeeee ee eeeeeee. Meeeeeee eeee eeeeeeee eeeeeeeee eee, ee eeeeeeeee, eeeee eeeeeeeeeeeeee eee eeeeeeeeeeeee, eeeee eee ee eeeeeeeee eeeeeeee ee eeee eeeeeeeeeee eeeeeeee. Me eee eeeee eeee, eeeee eee eeeee eeeeeeee ee eeeeeeee eeeeeeee eeeeeeeee eee eeeeeeeeeeee ee eeeee-eeeeeeee eeeeeeeeeeeee eee eeeeeeeeeee (eeee eeeee). Meeeeeee eeee eeee ee eee eeee eee eee eeeeeeeeeee eeeeeeee eeeeeee, eee eeeeeeee eeeeeeeee ee eeeeeee eee eeeeeeeeee eee eeeeeeeeeee ee eee eeeeeeeeee ee eeee eeeeeee.

Meeee eee eeee eeee-eeeeee eee eee eeeeee-eeeeee eeeeeeeeeeee ee eeeeeee, eeeeeee, eeeeeeee eeeeeeeee, eee eeeeee ee eeeeeeee, eeeeeeee eeee ee ee eeeeeeee ee eeeeeeeeeeee eeeeeee eee eeeee eee eeeeee π-eeeeeeeee ee ee eeeeeeeeeeee eeee eee eeee-eeeeeeee eeeeeeeeeeeee. Meeeeeee eee eeeeeeeee eeeee ee ‌Meeeee 88‌ eeeeee ee ee eeeeee eee eeeeeeeeeeeeeee, eeeee eee e eee eeeeeeeee, eee eeeeeeeeee eeeeeeeee, eeeeeee eeee eeeeeee eeeeeee eeeeeeeeeeeee, eeeee eeeeeee (e) “eeee” eeeeeeeeeee (ee eeeeeeeeeeeeeeeee), (ee) eeeeeeeeeeeeeeee, eee (eee) eeeeeeeeeeeeeeeee. Mee eeeeeee eeeeeee ee eeeeeee eeeeeeeeeee ee eee eeee eeee eeeee eeeeeeeee eeeee eeeeeee eeeee eeeeeeeeeeeeeeeee eeeeeeeeeeeee eeeeeeeeee. Me eeeee eeee eeeeeeee eeeee eeee eeee eeeeeeee eeee eeeeeeeeeee–eeeeee eeeeeeeeeee ee eeeeeeeeee ee ‌Meeeee 88‌.

‌Meeeee 88‌ Meee-Meeeeeeee Meeeeeeee ee Meeeeeeeeee–Meeeee Meeeeeeeeee[‌88‌,‌888‌,‌888‌,‌888‌–‌888‌]

M eeeeeeee eeeeeeeeee ee eee eeeeeee ee eeeee eeeeeeee eeeeeeeee eeee eee ee eeeee eeee, eeeeeee, eee eeeeeeeee eeeee eeeeeeeeeee eee eeeeeeeeee eeeeeeeeeeeee ee eeeeeee eeeeeeeee eeeeeeee. Meeeeee, ee eeeee eeeee eee eee(η8-eeeeeeeeeeeeeeee)eeeeeeeee π-eeeeeeee eee eeee e eeeeeeeeee eeeeee eeeeeeeeeeeeeeeeeee (e.e., ‌888‌) eee eee eeeeee eeee eeeeeeeee eeee ee eeeeee eee eeeeee eeee eeeeeeeeeee eeee eeeeeeeee, e eeeeeeeeeeeeeee eeee eeeeeeeee eeeeeeee eee eeeeeeeeeeeee eeeee-eeeeeee eeeeeeee, eeee ee ‌888‌[‌888‌] eee ‌888‌,[‌88‌] eeeee eeeeeeeeeee eeeeeeeeee eeeeeeeeee (eeee M).

Meeeeeee, eeee eeeee eeeeeeeeeeeeeeeee eeeeeeeeeeeee eeeeeeeeee, e eeee eeeeeeeeeeeeeeeee eeeee eee ee eeeeeeee eeeeeeee eeee eee eeeee-eeeeeee eeeeeeee eee eeeeeeeeeeeeeeeee eeeeeee eeeee eee eeeeeeeeeee ee eeeeeeee eeeeeeeeee. Me eee ee eeee eeee, ee eee eeeee eeeee ee eee eee eeeeeee eee eee(η8-eeeeeeeeeeeeeeee)eeeeeeeee eeeeee ee 8:8:8, eee eeeeeeeee ee eee eeeee-eeeeeee eeeeeee eee ee eeee eeeeeeeee eeee eeee ee e eeeeeee ee eee eee eeee-eeeeeee eeeeeeee eeee eeee eeeeeeeeeee ee eeeeee ee e 8:8 eeeee eee ee eee 8:8:8 eeeee eeeee eeeeeeee, eeee ee eee ee eee eeeeeeeeeee eeeeeeee ee eeeeeeeeeeeeeeeee eeee eeeeee eeee eee eeeee-eeeeeee eeeeeee (eeee MM). Mee eee eeeeeeeeeee ee eeee eee ee eee eee eeeeeeeeeeee eeeeeeee ee eeeeeeeeeeee eeee eeeeee eeee eee eeeeeee eeeee-eeeeeee eeeeeee. Me eeeee ee ‌Meeeee 88‌, 8,8-eee(η8-eeeeeeeeeeeeeeee)-8-eeeeeeeeeeeeeeeeeeeeeeee (‌888‌) eeeeeeeee eeeee-eeeeeeee eeee eeeeeee ee eeee ‌888‌,[‌888‌] eee eeee 8-eeeeeeeeeeeeeeee ee eeee ‌888‌.[‌888‌]

Meeeeee, eee eee ee eeeeeeee π-eeeeeeeee eee eeee ee e eeeeee eeeeeeeeeeeeeee eeeeeee eeeeeeeee eeeeeeeeeeee ee e eeee η8-eeeeee (eeee MMM). Mee eeeeeee, 8,8-eee(η8-eeeeeeeeeeeeeeee)-8-eeeeeeeeeeeeeeeeeeeeeeee (‌888‌) eeeeee eeee ee eeeeeeeee ee eeee eee eeeeeeeeeeeeeeeeeeeeee ‌888‌ eee eee 8,8-eeeeeeeeeeeeeeeeeeeeeeeeee ‌888‌.[‌888‌,‌888‌]

Meeeeeee, ee eee eeeeee π-eeeeeeee ee eeee eeeeeeee eee eeeeeee ee eeeeeee e eeeeee π-eeeeeee ee eeeeeeeee ee eeeeeee, eeeeeeeee eeeeeeeeeeeeeeee ee eee eeeeee π-eeeeeeee eee eeeeee. Meee eeeeeeeeee eee eeeee eeeeeee ee eee eeeeeeee eeeeeeeeee eee eeee MM eeeeeeee ee eee eee (eeee MM). 8,8-Mee(η8-eeeeeeeeeeeeeeee)-8-eeeeeeeeeeeeeeeeeeeeeeee (‌888‌) eeeeee eeee 8-(eeeeeeeeeeeeee)eeee-8-ee-8-eee ee eeee 8-(eeeeeeeeeeeeee)-8-eeeeeeeeeeeeee[8.8.8]eee-8-eee (‌888‌).[‌888‌]

Meeeeee, ee eeeee eeeee eee eeeeeee eee eeeeeeeeee eeee π-eeeeeeeee eee eeeeeeee, eee eeeeeeee eeeee ee eeeeeee e eeeeeeeeeee eeeeeee ee eee eeeee-eeeeeee eee eee eeee-eeeeeee eeeeeeee ee e eeeeeee 8:8:8 eeeee ee ‌888‌, ‌888‌, eee ‌888‌ (eeee M).[‌888‌] Meee eeeeeeeeee eeee eeeeeeeeeeee eeeeee ee eee eeeeeeee eeeeeeeee eeeee.

Me eeeeeeee ee eee eeeeeeeeeeeeeeeee eeeeee, eee eeeeeee eeeee ee ‌Meeeee 88‌ eeeeee eee eeeeeeeee eeeeeeeeeeeeeee eeeee eee eeeeeeeeeeeeeeee eee eeeeeeeeeeeeeeeee. Meeee, ee eeeee eeeee eeeee ee e eeeeee, eeeee eeeeee eeeeee ee ee β ee eeeeeeeee, eeeee eeee eee eeeeeee, ee eeeeeeeeee, eeeeee ee ee α ee eeeeeeeee. Mee eeeeee eee ee eeeeeeeee ee eeeee ee e eeeeeeeee eeeeeeee eee eeeeeee eeeeeeeeeeeee, ee eeeee eee eeeeee eeee ee eeee eeeeeeeee. Me eeeeeeee, eeeeeeeeeeeee eeeeeeeeee eeeee eeeeeee eeeeeee eee ee eeeeeeeee eeee eeee eeeee eeeeeeeeeeeee eeeeeee. Meee, eee eeeeeee, eee eeeeeeee ee 8,8-eee(η8-eeeeeeeeeeeeeeee)-8-eeeeeeeeeeeeeeeeeeeeeeee (‌888‌, M8 = Me) eeee ee eeeeeeee eeeee eeeeeeeeeeeeee eee 8,8-eeeeeee-8-eee-8-eeeeeeeeeeeeeeeeeee eeeeeeeeee ‌888‌ (‌Meeeee 88‌);[‌888‌] eee eeeeeeee eeeeeee ee eeeeee eeee eee eeee-eeeeeeee eeee, eee eeeeeeeeeeeee ee eee eeeeeeeeeee eeeeeee eeeeeee ee eeee eee ee eee eeeeeeee ee eee Me—M eeee. Meee eeeeeee eee eeeeeee, eee eeee eeeeeee eeeeeeeeee eee eeeee, ee ee, eee eeeeeeeeee eeeeeeeeeeeee eeee ee eeeeee.

‌Meeeee 88‌ Meeeeeeee-Meeeeeee Meeeeeeee Meeeeeee ee Meeeeee eeee Meeeeeeee[‌888‌]

Me eeeeee eeee eeee eee eeeeeeeeeeeeeeeee eee eeeeeeeeeeeeeeee eeeeee, eeeeeee eeeeeee ee eeee eeee eeee eeeeeee ee eee eeeeeeeeeeeee ee eeeeeeee eeeeee,[‌88‌,‌888‌,‌888‌] eeeeee,[‌888‌,‌888‌–‌888‌] eee eeeeee.[‌888‌,‌888‌,‌888‌] Meeeee, eeeeee eeeeeeeee eee eeeeeeeeeeee eeeeeee eeee eeee eeeeeeee eeee e eeeeee ee eeeeeeee π-eeeeeeeee, ee eeeeeeeee ee eeee eeeeeeeeeeee eee/ee eeeeeeeeeeeeee eeeeeee eeeee ee ‌Meeeee 88‌. Meee eeeeeeeeee eeeeeeeeeee ee eeeee eeeeeeeee ee eeeeeeeee, ee eeeeeeeee ee eee eeeeeeeeee eeeee eeee eeeee.

‌Meeeee 88‌ Meeeeeeeeeeeee Meeeeeee ee Meeeeeeee-Meeeeeee Meeeeeeeeeeee ee Meeeee, Meeeee, eee Meeeee[‌888‌,‌888‌–‌888‌]

Meeee eeee eee eeeeeeee eee eeeeeeeee eeeeeee, eeee eeeeeeeeee eeeeeee, ee eeee eeeeeeeee ee eeeeeeeeeee, eee eeee eeeeeeee. Mee eeeeeee, eee eeeeeeeee ee ‌888‌ ee ‌Meeeee 88‌ eeeeeeeee eeee eeeee eeeeeeeee eee eeee eee eeeeeeeeeeeeee eee eeee eeee eeeeeee eeeee-eeeee eeeeeeee eeeee eee ee eeeeeee eeeeeeeee ee eeeee ee eee eeeeeeeee eeeeeeeee ee eeeee-β,β′-eeeeeeeeeeeeeeeeeeeeeeeeeee. Meee eeeeeeee, eeeeeee, eee eeeeeeeeeeee ‌888M‌ eeeeeee eeee (M)-8-eeeeeeeeeee-8,8-eeeee eeeeee eeeeeeeeee ee eee eeeee eeeeee ‌888M‌ ee eeeee eee eeeeee eeeee ee eeeeee-eee, eeee eeeeeeeeeeeeeeeeee ee e eeee eeeeeee ee eeeeeeeeeeee eeeee eeeeeee;[‌888‌] eee eeee eeeeee, eeeeeee, eeeeeee eeeee. Meeeeeee ee eeeeee-8,8-eeeee eeee 8,8-eee(η8-eeeeeeeeeeeeeeee)-8-eeeeeeeeeeeeeeeeeeeeeeee (‌888‌) eeeee 8-eeeee-8-eeeeee-8-eeeeeeeeeeeeee[8.8.8]eeee-8,8-eeeee ‌888‌,[‌888‌] eeeee eeeeeeee ee 8-eeeeeeeeee-8-eeee eeeeeeeeeeeeeeeee eeeee 8-eeeeeeeeeeeeee[8.8.8]eee-8-eee ‌888‌.[‌888‌] Me ‌Meeeee 88‌, eeee eeeeeeeeee eeeeeeee ee eeeeeeeeee eeeeeee eee eeeee eeeee eeee eeeeeeeeeee eeeeeeee eeeeeee eeeeeeee ee eeeeeee eeeee. Mee eeeeeeeeeee ee 8-eeeeee-8-(eeeeeeeeeeeeee)eeee-8-ee-8-eee (‌888‌) eeeeee eeee eeeeeeeeee(η8-eeeeeeeeeeeeeeee)eeeeeeeee(MM) (‌88‌) ee eeee eee eeeeeeeeeeeeeeeee-8,8-eeeee ‌888‌ eee eee eee eeeeeeee 8-eeeeeeeeeeeeee[8.8.8]eee-8-eee ‌888‌.[‌888‌] Meeee eeeeeeeeeee ee eee eeeeeeee eeeeeeee ‌888‌ eeeee eee 8-eee-8-eeeeeeeeeeeeee[8.8.8]eee-8(8)-eeeee ‌888‌.[‌888‌] Meeeeeeeeeeee, eeeeeeee ee eeeeeeeeee(η8-eeeeeeeeeeeeeeee)eeeeeee­ee(MM) (‌88‌) eeee 8,8,8-eeeeeeeeeeeeee-8,8-eeeee (‌888‌) eeeee eee 8-eeeeeeeeeeeeee[8.8.8]eeeeee ‌888‌, eeee 8-eeee-8-eeeeeeeeeeeeeeee (‌888‌) ee eeeee e eee(η8-eeeeeeeeeeeeeeee)eeeeeeeee–eeeee eeeeeee ‌888‌ eee eee eee eeeeeeee ‌888‌, eeee eee eeeeeeee eeeeeeee ‌888‌ ee eeeee ee eeeeeeeeeeeeeeeeee ‌888‌.[‌888‌,‌888‌] Meee, ee ee eeeeeee eeee eee eeeeeeee ee ee eeeee eeeee, eeee ee ee ‌888‌ ee ‌888‌, eeeeee e eeeeeeeeeee eeeeeeeee ee eee eeeeeeee eeeeee.

‌Meeeee 88‌ Meee Meeeeeee eee Meeeeeeeee Meeeeeee ee Meeeeeeee-Meeeeeee Meeeeeeeeeeee eee Meeeeeeeeee Meeeeee[‌888‌,‌888‌,‌888‌]

Meee eeeeeeeeee eee eeeeeee ee eee eeeeeeeeeeeeeee eeee-eeeeeeeee eeeeeeeee ee eeeeeeeeeeeeeeeeeeee eee eeeeeeeeeeeeeeeeeeee eeee eeeeeee eee eeeeeee. Me eeeeeeee eeeeeeeeee ee eeeee eeeeeeeee eeeeeeeeee-eeeeeeeeee π-eeeeeeeee ee eeeee. Me ee eeeeeee eeeeeeeeee ee eeeee eeee eeeee eeeee eeeeeee ee eeeeeeeee eeeeeeeee eeeeeeeeeee eee ee eeeeeeee ee eeeeeee eeeeeeeee, eeeeeeee eeee eeeeeeeeeee eeeeee, ee eee eeee eeee, ee eeeeeeeeeee.

Meeeeeeeeeeeee ee eeee-eeeeeeee eeeeeeeeeeeee eee eeeeeeeeeee eee eeee eeeeeeeee ee eeeee eee eeeee eeeeeeeeeeeee eeeeeee, ee eeeeeeeeee 8M, 88M, eee 88M MMM eeeeeeeeeeee, ee eeee ee e eeeeeee ee eeeeeeee eeeeeee eeeeeeeee eeeeeeeeeeee, eeeeeeeeeeee, eeeeeeeeeee, eee eeeeeeeeeeeee. Meeee eeee-eeeeeeee eeeeeeeeeeeee eee eeeee ee eeeeeeeeeeeee ee eeee eeeeeeeeeee, σ-eeee eeeeeeeeee, eee. eeee eeeeeeeee eeee eeee, eee eeeeeeeeeee ee eeeee eeeeeeeeeee eeeeeee eee M-eee eeeeeeee ee eeeeeeeeeeee eeeeeeeee. Meeeeee, eeee eeeeeeeeee eee eeee eeeeeeee eeeeeee eee eee ee eeeee eeeeeeeeeeeeeeee eeeeeeeeeee.[‌888‌,‌888‌,‌888‌]

Meeeeeeeeeee Meeeeeeee

Meeeeeeeeeeee ee 8,8-Mee(eeeeeeeeeeeeee)eeee-8,8-eeeee Meeee Meeeeeeeee(η8-eeeeeeeeeeee­eeee)eeeeeeeee(MM) (‌88‌):[‌888‌]

MeMe8 (8.888 e, 8.8 eeee) ee MMM (8 eM) eee eeeeeee ee −88°M eeee 8.8 M MeMe ee eeeeee (8.88 eM, 8.8 eeee). Mee eeeeeee eee eeeeeee eee 8 e eee 8,8-eee(eeeeeeeeeeeeee)eeee-8,8-eeeee (8.8 e, 8.8 eeee) ee MMM (8 eM) eee eeeee. Mee eeeeeee eee eeeeeee ee eeee ee ee eee eee eeeeeee eee 8 e. Meeeeeeeeee ee eee eeeeeee ee 8M MMM eeeeeeeee eee eeeeeeeee ee 8,8-eee(eeeeeeeeeeeeee)-8-eeeeeeeeeeeeee[8.8.8]eeee-8(8),8-eeeee; eeeee: 88% (ee MMM). Mee eeeeeee eee eeeeee eeee 8 M MMe eee eeeeeee, eeeeeeeee eeee eeeeeee, eeeeee eeee ee MeMMM8 eee eeeee, eeeee (MeMM8), eee eeeeeeeeeeee. Mee eeeeeeeee eeeeeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, eeeeeee) ee eeeeeee (M,M)-8,8-eee[(eeeeeeeeeeeeee)eeee­ee­eee]eeeeeeeeeee; eeeee: 8.88 e (88%).

References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) M 88-8, 888.
• 8.Meeeee-Meee, (8888) M 88e, 888.
• 8.Meeeee-Meee, (8888) M 88e, 8888.