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Please login to access the full content or check if you have access via1.4.1.8.4 Inter- and Intramolecular [2+2+2] Cyclization of Diynes with Heteroatom-Substituted Multiple Bonds
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Malacria, M.; Aubert, C.; Renaud, J.-L., Science of Synthesis, (2001) 1, 458.
Cyclopentadienone complexes may be obtained not only by carbonylation of isolated metallacyclopentadienes but directly from the intermolecular reaction of two alkynes and dicarbonyl(η5-cyclopentadienyl)cobalt(I) (1). It has been found that trimethylsilylalkynes or alkynes bearing polar electron-withdrawing substituents undergo such reactions under low-temperature photolytic conditions in the presence of stoichiometric amounts of 1 to furnish complexed cyclopentadienones with good regioselectivity.[95] For example, complex 48 was the major product in the cyclization of trimethylsilylacetylene with 1 (Scheme 25), whereas the corresponding 2,4-disilylated product 49 predominated when dicarbonyl(η5-pentamethylcyclopentadienyl)cobalt(I) was employed.
Meeeee 88 Meeeeeeee ee Meeeeeeeeeeeeeeee Meeeeeeee[88]
Mee eeeeeee ee eeeee eeeeeeeee eeee ee eeeee eeeee eeeeeeeeeeeeee eeeeee eeeeeeeeeeeeeeeee ee eeeee eeeee eeeee (Me8+) ee eeee eee eeee eeeeeeeee eeeeeeeeeeeeeeeeee, eeeee eeeeeeee ee eeeeeeeeeeeeeee eeeeeeee eeeeeeeeee ee eeeeeee eeeeeeeeeeeeeee.
Meeeeeee eee eeeeeeeeeee ee α,ω-eeeeee eeee eeeeeee eeeee ee eeeeeeeee ee eeeeeeeeeee (eee Meeeee 88), eee eeeeeeeeeeeeeee ee ee eeeeeee–eeeeee eeee eee(eeeeeeeeeeeee)eeeeeeeee eee eeee eeeeeeeeee (88% eeeee) eee eeeeeee e eeeeee eeeeeeeee ee γ-eeeeeeee (Meeeee 88).[88] Mee eeee ee ee eeeeeee eeee eeeeeeeee ee eee eeeeeee eee [MeMe], eee eeeeee eeeee ee π-eeee eeeeeeeeeeee eeee ee eeeeee,[88,88] eeeeeee,[88] eeeeeeeee (eeeee eeeeee ee eee M=M eeee eee eee ee eee M=M eeee),[888] eeeeee,[888,888] eeeeee, eee eeeeeeeeee[888] eeeeeeeeeee ee eeee, eeeeeee eee eeeee eeeee ee eeee eeeeee (Meeeee 88). Me eeee eeeee, eeeeee eeeeeeeeeeeeeeeeee eee eeeeee eeeeee eeee eeee eeeeeeee ee eeeee eee eeee eeeeee eeeeeeee eeeeeeeeeeeeeeeeeee(eeeeee)eeeeee(M) (8) eeeeee eeee eeeeeee 8.
Meeeee 88 Meee Meeeeeee ee Meeeeeeeeeeee ee Meeeee eeee Meeeeeeeee-Meeeeeeeeee Meeeee Meeee[88,888]
Meeeeeeeeee eee eeeeeeeeee eeee eee [8+8+8] eeeeeeeeeee ee eee eeeeeee eee eee M=M eeee ee eee eeeeeeeeee eeeee (Meeeee 88). Meee eeeeee(M) eee eeeeee(8)[888,888] eeeeeee eeeeeeee eeee eeeeeeee, eee eeeeeeeeeee eeeeeeeeeee ee eee eeeeeeeee eee eee eeeeeeeeeee eee eeeeeeee. Mee eeeeee eeeeeee eeeeee ee eeeeeee eeeeeee eee eeeee eeeeeeeeeeeeeeeeeeeeee eeeeeeeeeeee eeeeeeee ee eeeeeeeee ee eee eeeeeeeeee.[888,888] Me ee eee eeee ee eee eeeeeeeeeeeee ee eeeeeeeeeeeee eeeeeee, e eeeeeeeeee ee eeeee eee eeeeeee eeeeeeeee eeeeeee eee eeeeeeeeeeee eeee eeeeee eeeeee ee eeeeeeeee 8 eee 8. Mee eeeeeeee eeeeeeeeeeeeeeeeeee(eeeeee)eeeeee(M) (8) ee eeeeee eee eeeeeeee eeeeeee eee eeeee eeeeeeeeeee eee 8,8-eeeeeeeeeeeee eeeeeeeee eeee ee eeee eeeeeeeeeee ee eeeeeee ee eeeeee eeeeeeeee.[888] Meeee eeeeeeeee eeeeeeeeeeeeee eeeeeeee ee eeee eeeeeeeeeee, α,ω-eeeeee eeeee eeee ee eeeeeeeeee ee eee eeeee ee eee eeeeeeee ee eeeeee eeeeeeeeee 8 ee 8. Me eeeeeeee, eee eeeeeeeeeee ee α,ω-eeeeeeeeeeeeeeeee eeee eeeeeee eeeeeeee eeeeeeee ee eee eeeeeeee ee eeeeeee 8 eeee eeee eeeee- eee eeeeeeeeeeeeeeee ee eeee 8,8-eeeeeeeeeeeeeeee-8(8M)-eeee (Meeeee 88).[888]
Meeeee 88 Meeeeeeeeeeee ee Meeeee eeee Meeeeeeeeee[888,888]
Mee eeeeeeeeeee ee eee eeeeeeeeee ee eeeeeeeeeeeee ee eeeee eeeeeeeee eeeee e eeeeeeeee eeeee eeee eee 8-eeeee-8,8-eeeeeeeeeeeeeee eeeeee.[888,888,888]
Mee eeeeeeee eeeee ee ee eeeeeeee ee eeeeee eee eeeeeeeee eeee eee eeeeeee ee eee eeeeeeee ee e eeeeeeeeeeeeee eeeeee ee eeeeee eeeeeee 8 ee 8 (Meeeee 88).[888,888] Mee eeeeeeee eeeeeeeeeeeeeeeeeeeeee–eeeee eeeeeeeee eee eeeeee ee eee eeeeeeeeee ee eeeee eeeeeeeee, eee ee eeee eeeee eeeeeeee eeeeeeeeeeeeeeeeeeeeee–eeeee eeeeeeeee, ee eeeee e M—M eeee ee eee eeeee eeee eee eeee eeeeeee, eee eeeeeeee.[888] Meee eeeeeeeeeeeeeee eeeeeee e eeeeeeee eeeeeeeeeee ee eee Meeee–Meeee eeeeeeee ee eeeeeeeeeeeeee eeeeeeeeeee.
Meeeee 88 Meeee- eee Meeeeeeeeeeeee [8+8+8] Meeeeeeeeeee ee Meeeeee eeee Meeeeeeee ee Meeeeee[888]
Meeeeeeeeeee Meeeeeeee
8,8-Meeeeeeeeeeeeeee-8(8M)-eeee; Meeeeee Meeeeeeee:[888]
Mee eeeeee (8 eeeee) eee eeeeeeeee ee e-eeeeee (88 eM) ee e 88-eM eeeee-eeeeeeee eeeee [eeeeeeeeee eeee (MMM)8MM] eeeeeeee eeee e eeee eeeeeeeee. Meee eeeeeee eee eeeeeeee eeeee eeeee eeeeee–eeee–eeee eeeeee eee eeeeeee ee eeeeee (eee eeee) eeeee M8. Mee eeeeeeeeee (8 eeeee) eee eee eeeeee (8–8 eeeee) eeee eeeeeeeee ee eeeeeeee e-eeeeee ee e eeeee eeeeee ee 8 eM eee eeeeee eeee e 8-eM eeeeeee. Me eeeeeee 8-eM eeeeeee eee eeeeee [MeMe(MM)8] (8; eeeeeeeee 8.88 eeeee) ee eeeeeeee e-eeeeee (8 eM). Mee eeeeeeee ee eeee eeeeeeee eeee eeee eeeee ee eee eeeeeeeeee eeeeeee eeeeeee eeeeeee ee e eeee ee 8 eeee·e−8 eee e eeeeeee eeee. Meeeee eee eeeeeeee eee eeeee eee eeeeeeeeee eeee e eeeee eeeeeeeee eeee (888 M) ee e eeeeeeee ee eeeee 8 ee eeee eee eeeeee ee eee eeeee. Meeeeee eee eeeeeeeeeee eeee eeeeeeeee eee 88 eee eeeee eee eeeeeeee eee eeeeeeee. Mee eeeeeee eee eeeeee eee eee eeeeeeeee eeee eeeeeee ee eeeeee eeeeeeee. Mee eeeeeee eee eeeeeeeeeee ee MeMMe eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe eeee 8–88% MeMM). Mee eeeeeeeee eeeeeeee eeee eeeeeeeeeeeeee eeee eeeeeeee ee eeeee, ee eeeeeee eeeeeeee eee eeeeeeeeeee MMM eeee eeeeee.
Meeeeeeeeee ee Meeeeee eeee Meeeeeeee ee Meeeeee; Meeeeee Meeeeeeee:[888]
Mee eeeeeeeee eee eee eeee ee eee eee eeeeeeeee ee 8,8-eeeeeeeeeeeeeeee-8(8M)-eeee. Mee eeeeeeeee eeeee 8, eee eeeeeeeeee eeee eeeee eee eeeeeee ee e eeee ee eee eeeeeee.
References
[95] | Meeeee, M. M. M.; Meee, M. M.; Meeeeeeee, M. M. M., Meeee. Meee., (8888) 88, 8888; Meeee. Meee. Mee. Me. Meee., (8888) 88, 8888. |
[96] | Meeeeeee, M. M.; Meeeeeeee, M. M. M., Meeeeeeee, (8888), 888. |
[97] | Meeeeeee, M. M.; Meeeeeeee, M. M. M., M. Me. Meee. Mee., (8888) 888, 8888. |
[98] | Meeee, M.; Mee Meeeee, M. M.; Meeeeeeee, M. M. M., Meeeeeeee, (8888), 8888. |
[99] | Meeeeeee, M. M.; Meeeeeeee, M. M. M., M. Mee. Meee., (8888) 88, 8888. |
[100] | Meeee, M.; Meöeeee, M.-M.; Meeeeeeee, M. M. M., Meeee. Meee., (8888) 88, 8888; Meeee. Meee. Mee. Me. Meee., (8888) 88, 8888. |
[101] | Meeee, M.; Meeeeeeee, M.; Meeeeeeee, M. M. M., Meeee. Meee., (8888) 888, 8888; Meeee. Meee. Mee. Me. Meee., (8888) 88, 888. |
[102] | Meeeeeeeee, M.; Meeeeeeee, M.; Meeeeeeee, M. M. M., Meee. – Mee. M., (8888) 8, 8888. |
[103] | Meeee, M.; Meeeee, M. M.; Meeeeee, M. M.; Meeeeeeee, M. M. M., M. Me. Meee. Mee., (8888) 888, 88888. |
[104] | Meeeee, M.; Meeee, M. M., M. Meeeeeeee. Meee., (8888) 888, 888. |
[105] | Meeeee, M.; Meeee, M. M., Meeeeeeee, (8888), 888. |
[106] | Meee, M.; Meeeeeee, M., Meeeeeeee, (8888), 88. |
[107] | Meee, M.; Meeeeeee, M., Meeeeeeeeee Meee., (8888), 8888. |
[108] | Meeeeee, M.; Meeeeeee, M.; Meeeeeeee, M.; Meeeeeee, M., M. Mee. Meeee., (8888) 88, 888. |
[109] | Meee, M. M.; Meeeeeeee, M. M. M., M. Mee. Meee., (8888) 88, 8888. |
[110] | Meeeee, M.; Meeeeeee, M., Meeeeeeee, (8888), 888. |
[111] | Meeeeee, M.; Meeeeeeeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[112] | Meeeee, M. M.; Meeeeee, M. M.; Mee, M. M.; Meeeeeeee, M. M. M., Meeeeee, (8888), 88. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) M 88-8, 8888.