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46.5.2.2.4 Variation 4: Cobalt-Mediated Cycloaddition

DOI: 10.1055/sos-SD-046-00090

Gandon, V.; Thorimbert, S.; Malacria, M.Science of Synthesis, (200946190.

Although cyclohexa-1,3-dienes are good ligands for transition metals, catalytic methods using these metals for the formation of cyclohexa-1,3-dienes are relatively scarce and are often restricted to specific substrates.[‌20‌,‌56‌,‌72‌‌84‌] However, when used in stoichiometric amounts, cobalt complexes prove to be the reagents of choice for mediating direct alkyne/alkene cocyclizations that take place in a highly chemo-, regio-, and stereoselective manner, and exhibit broad substrate tolerance.[‌54‌‌60‌,‌85‌] The mechanism for such reactions has been studied by means of density functional theory (DFT) computation.[‌39‌] Although the reported cyclizations ultimately furnish the desired organic products complexed to cobalt, this outcome is advantageous as it stabilizes the ligands against isomerization or aromatization and, at the same time, potentially activates them toward hydride abstraction, and further substitution.[‌34‌,‌86‌,‌87‌] In some cases, however, unexpected rearrangements of the (η5-cyclopentadi­enyl)cobalt-complexed diene framework may occur.[‌75‌]

Me eeeee ee 8888 ee eee eeeeeeee eeee eeeeeeeeeeeeeeee eeeeeeeeeeeeeeeeeeeeeee 88, eeeeeeee eeee (η8-eeeeeeeeeeeeeeee)eee(eeeeeeeeeeeeeeeeee)eeeeee(M) ee eee eeeeeeee eeeeeeeeeeee ee eeeeeeeeeeeeeeeeee eeeeeee ee eeeeeee (eee eeeeeee 88), eeeee eeee eeeeeee ee eeee η8-eeeeeeeee-8,8-eeeee eeeeeeeee ee eee eeee 88. Mee eeeeeeeeeeeeeeeeeeeeee eeeeeeee eee eeeeeeeeeeee ee eeeeeee ee eeeeeeeee eeeeeeeeeeee eeeee e eeeeee(MM) eee eeeeee (Meeeee 88).[‌88‌]

Meeeee 88 Meeeee-Meeeeeee Meeeeeee Meeeeeeeeeee ee Meeeeeeee-8,8-eeeeee eeee Meeeeee eee Meeeeee[‌88‌]

Mee eeeee eeeeeeee eee ee eeeeeeeee ee eeee, eeeeeeeee (η8-eeeeeeeee-8,8-eeeee)(η8-eeeeeeeeeeeeeeee)eeeeee eeeeeeeee ee e eeeeee eeee. Meeeeeee, eeeeeeee eeeeeeeeeee ee eeeeee,[‌88‌] eeeeeeeeee,[‌88‌] eeeeeeeeee,[‌88‌,‌88‌] eeeee, eee eeeeeeeee,[‌88‌] ee eeee ee eeeeeeeee eee eeeeeee[‌88‌] eee eeee ee eee eeeeee eeeeeeee ee eeeeeee eeeeeeeeeeeeee. Meeee eeeeeeeeeeeeee eeeeeeeee eeee eeee eeee eeeeeeee[‌88‌‌88‌] eee, eee eeeeeee, 8 eeeee eeeeeeeeeee ee e eeeeeee eeeeeeeeeeeeeee 88 eee 8 eeeeeeeeee ee ee eeeeee eeeeeee eeee (η8-eeeeeeeeeeeeeeee)­eee(eeeeee)eeeeee(M) ee eeee eeeeeeeee eeeeeeee eeeeeeeee-8,8-eeeeee 8888, eeeeeeeee eeee e eeee eeeee ee eeeee-, eeeee-, eee eeeeeeeeeeeeeeeeeeee (Meeeee 88).

Meeeee 88 Meeeee-Meeeeeee Meeeeeeeeeeeee eeeeeee Meeeeee Meeeeeeeeeeeeeee eee Meeeeee[‌88‌,‌88‌]

Meeeeeeeeee 88

M8 M8 Meeee Meeee (%) Mee
Me M (88/88) 8:88 88 [‌88‌,‌88‌]
MM8MMe M (88/88) 8:8 88 [‌88‌,‌88‌]
MM8MMe M (88/88) 8:8 88 [‌88‌]
Me Me eeee-88 eeee 88 [‌88‌,‌88‌]
Me Me-Me eee-88 eeee 88 [‌88‌]
Me MMMM (eee-88/eee-88) 8:8.8 88 [‌88‌]
Me MMee (eee-88/eee-88) 8:8.8 88 [‌88‌]

Meeeeee eeeeeeeee eeeee eeeeee eeeeeee eeeeee eeeeee eeeeeeeee ee eeee 88 ee eeeee eeeeeeeeeeee (Meeeee 88)[‌88‌,‌88‌] eee, ee eee eee eeeeeee eeeeeeee eeee eeeeeee eeeeeee, eeeee eeeeeeee eee ee eeeeeeeee ee eeeeeeeee eeeeeeeeeeee. Mee eeeeeeeee eeeee-eeee eeeeeeeee­eeeeee eee eeee ee eeee ee MeeeeeMeeeeee eeeee-eeeeeeee eeeeeeeee.[‌88‌]

Meeeee 88 Meeeee-Meeeeeee Meeeeeeeeeeeee eeeeeee Meeeeeeeeeeeeeee eee Meeeee Meeeeee[‌88‌,‌88‌]

α,ω-Meeeee eeee eeeeeeeeeee ee eeeeeeeee eeeeeeeeeee eeeeeeeeeeeeee ee eeee eeeee eeeeeee (Meeeee 88) eeeee eeeeeeeeeee eeeeee eee eeeeeee eeeeeee[‌88‌,‌88‌] ee eeee ee 8,8-eeeeeeeeeeee ee eeeee eeeeeeeeeeee eeeeeeeeee e eeeeeeee eeeeee eeee. Mee eeeeeee, eeeeee-eeeeeeee [8+8+8] eeeeeeeeeeeeee eeeeeee α,ω-eeeeee eee eeeeeeeeee eeeeeeeeeee eeeee (η8-eeeeeeeeeeeeeeee)eeeeee-eeeeeeeee 8e,8e-eeeeeeeeeeeeeeeeee-8,8(8M,8M)-eeeeee eeee ee eeeeeee 88 (M=MM8; M=M).[‌88‌] (η8-Meeeeeeeeeeeeeee)eeeeee-eeeeeeeee 8M-eeeeee eeee ee eeeeeeee 88 eee eeee ee eeeeeeee eeee eeeeeeeee eee eeeeeee,[‌88‌] eee eee 8,8-eeeeee eeee ee eeeeeee eeeeee eeee eeeeeeeeeeeeee eeee eeee (η8-eeeeeeeeeeeeeeee)eeeeee-eeeeeeeee eeeeeeeeeeeeeeeee 88.[‌88‌]

Meeeee 88 Meeeeeee Meeeeeee ee Meeeee-Meeeeeee Meeeeeeeeeeeee eeeeeee Meeeee eee Meeeee Meeee[‌88‌,‌88‌,‌88‌,‌88‌]

Meeeee eeeeeeeeeee eeeeeeeeeeeeee eeeeeee eeeeee eee eeeeeee (eeeeeeeee eee eeeeee eee eeee ee eee eeeeeee ee eeee ee eee eeeeeeeeee) eee ee eeeeeeee, eeeeeeeee eeeeeeeeee eeeeeeeee eeee eeee eeeeeeeeeee. Meeeee, eeeeee-eeeeeeee [8+8+8] eeeeeeeeeeeeee ee M-ee­eee­eeeeee eeeeee eeeeeeeeeee 88 eee eeeeee eeeeeee eeeee eeeeeeee eeeeeeeeeee 88 eeee eee eeeeeeee eeeeeeee eee eeeeeeeeee eeee eeeee,[‌88‌,‌88‌] eeeeeee 8e,8e-eeeeeee-8M-eeeeeeeeee 88 eee ee eeeeeeeee eeeeee eeee M-(eeee-8-eeeee)eeeeeee 88 eeeee eeeeeee eeeeeeeeee (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeee Meeeee-Meeeeeee Meeeeeeeeeeeee ee Meeeee eee Meeeeee[‌88‌,‌88‌,‌88‌]

Meeeeee eeeeeeeeee eeeeeeeee-8,8-eeeeee 88 eee ee eeeeee eeee eee eeeeeeeeeee eeeeeeeee 88 eeeeeee eeeeeeeeeeeeee eeeeeeeeeeee eeeee (η8-eeeeeeeeeeeeeeee)eee(eeeeee)eeeeee(M) ee eeeeeeeeeeeeeee ee eeee eeeeeeeeeee,[‌88‌] ee eeeeeeeeee(η8-eeeeeeeeeeeeeeee)eeeeee(M) ee e eeeeeeeeeee eeeeeee ee eeeeee.[‌88‌,‌88‌,‌88‌] Meeeeeeeeeeee, e eeeeeeeeeee ee eeeeee(MM) eeeeee, eeeeeeeeeeeeeeeeee, eee eeeeeeeee ee eeeeeeeeeeeeeee ee eeee eeeeeeeeeee eee eeee ee eeeeeeee ee eeee eeeee[‌88‌] (Meeeee 88).

Meeeee 88 Meeeeeeeee-Meeee Meeeeeeee-8,8-eeeeee eeee Meeeeeeee[‌88‌,‌88‌,‌88‌‌88‌]

Meeeeeeeeee 88

M M8 M8 e Meeeeeeeee Meeee (eeee/eee) Meeee (%) Mee
MM8 M M 8 Me(Me)(M8M=MM8)8, MMM, ee, 8e 88 [‌88‌]
(MM8)8 MMM M 8 Me(Me)(MM)8, 8,8,8-eeeeeeeeeeeeeeee, eeeeee, 88e eeee eeee 88 [‌88‌,‌88‌]
M MMM M 8 Me(Me)(MM)8, 8,8,8-eeeeeeeeeeeeeeee, eeeeee, 88e eeee eeee 88 [‌88‌,‌88‌]
(MM8)8 MMM M 8 Me(Me)(MM)8, 8,8,8-eeeeeeeeeeeeeeee, eeeeee, 88e 8:8 88 [‌88‌,‌88‌]
(MM8)8 M MM8Me 8 Me(Me)(MM)8, eeeeee, eeeeee, eeeeeeeee 8:8.8 88 [‌88‌]
(MM8)8 M MM8Me 8 Me(Me)(MM)8, eeeeee, eeeeee, eeeeeeeee 8:8.8 88 [‌88‌]
M(MM8Me)8 M M 8 MeM8 (8eeeee), Me8M (8eeeee), Me (88eeeee), MM8Me8, ee 88 [‌88‌]

Meeeeee eeeeeee 88 eee eeeeeeeee eeee eee M-eeeeeeeee 88 eee eeeeeeeeee(η8-eeeeeeeeeeeeeeee)eeeeee(M) ee eeeeee eeeeeee ee e-eeeeee eeeee eeeee ee eeee ee eeee ee eeeeee eee eeeeeeeeeeee. Meeeeee eeeeeeeeee eee eeee eeee ee eeeeeee eeeee ee eeeeeeee eeeeeee 88 eeee eee (M)-eeeeeeeee 88 (Meeeee 88).[‌88‌,‌88‌] Mee eeeee ee eeeee eeeeeeeeee eee eeeeeeeee eee eeeee eeeeeeeeeeeeeee, eee eeee eee ee eeeeeeeeeeee eeeeeee eee eee eeeeeeeee ee eeeeeeee (eee Meeeeee 88.8.8.8).[‌88‌,‌888‌‌888‌]

Meeeee 88 Meeeeeeee ee Meeeeeeee Meeeeeeee-8,8-eeeeee eeee Meeeeeeee[‌88‌,‌88‌]

Meeeeeeeeeee Meeeeeeee

(η8-Meeeeeeeeeeeeeee)[8,8-(8,8-eeeeeeeeeeeeeeeee-8,8-eeeee-8,8-eeee)eee(8,8,8,8-eeeeeeeeeee-8,8,8-eeeeeeeeeeeee)]eeeeee(M) (88, M8=Me; M8=M); MeeeeeeMeeeeeeee:[‌88‌]

[Me(Me)(M8M=MM8)8] (888ee, 8eeee) ee MMM (8eM) eee eeeeeeeee eeeee eeeee eee eee eeee eee eeeeee ee 88°M. Mee eeeee eeeeeeeeee eee eeeeeeee ee eeeeee, eee eeee eee eeeeee 88 (M8=Me; 888ee, 8eeee) ee MMM (8eM) eee eeeeeeeeeee ee eeeee ee e eeeeeee eeee eee eeee eeeeeee. Mee eeee eeee eee eeeeeee eee eee eeeeeee eee eeeeeee ee ee eee 8e, eeeeee eee eeeeeee eee eeeeeee eeeee e eeeeee eeeeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee [eeeeee eee, eeeeeeee eeeeeeee ee eeeeeee eee Me8M (eeee eee eeeee)] ee eeeeee eee eeeee eeeeeeee ee e eee eeeee; eeeee: 8.88e (88%).

(η8-Meeeeeeeeeeeeeee)[8,8-(8,8,8-eeeeeeeeeeeeeeeeee-8,8-eeeee-8,8-eeee)eee(8,8,8,8-eeeeeeeeeee-8,8,8-eeeeeeeeeeeee)]eeeeee(M) (88, M8=M8=Me); MeeeeeeMeeeeeeee:[‌88‌]

[Me(Me)(M8M=MM8)8] (888ee, 8eeee) eee eeeeeeeee ee MMM (8eM) eee eeee eeeeeee (8.88e, 8eeeee) eee eeeee. Mee eeeeeee eeeeeee ee eeee eee 8e ee ee, eee eeee ee eee eeeeee ee 88°M ee eee eeeeee 88 (M8=Me; 888ee, 8eeee) ee MMM (8eM) eee eeeeeeeeeee eeee ee ee eeeee ee e eeeeeee. Mee eeee eeee eee eeeeeee eee eee eeeeeee eee eeeeeee ee ee eee 8e, eeeeee eee eeeeeee eee eeeeeee eeeee e eeeeee eeeeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee [eeeeee eee, eeeeeeee eeeeeeee ee eeeeeee eee Me8M (eeee eee eeeee)] ee eeeeee eee eeeee eeeeeeee ee e eee eeeee; eeeee: 888ee (88%).

(η8-Meeeeeeeeeeeeeee)[(8,8e,8e,8-η)-(8e-eeee,8e-eeee)-8,8-eeeeeeee-8,8,8,8e-eeeeeeeeee[e]eeeeeeeeeee-8,8(8M,8eM)-eeeee]eeeeee(M) (88, M=MM8; M=M); MeeeeeeMeeeeeeee:[‌88‌]

8,8-Meeeeeeeeeeeeeeeeeeeeeeee-8,8(8M,8M)-eeeee (8.888e, 8.888eeee) eee eeeeeeeee ee eeeeeee (88eM) eeeeeeeee ee e eeeee-eeeeeeee eeeee (88eM) eeeeeeee eeee e eeee eeeeeeeee. Meee eeeeeee eee eeeeeeee eeeee M8 ee eeeee eeeeeeeeeeeeee eeeeee ee e eeeeee eeee, eee eeee eeeeeee ee eeee ee ee. Meeee-8,8-eeeee (8.888e, 8.88eeee) eee eeeeeeeee ee eeeeeee (8eM) eee eeeeeeee ee eeeeee, eee eeee Me(Me)(MM)8 (8.888e, 8.88eeee) eee eeeee ee eeeee ee e eeeeeee. Mee eeeeeeeee eeee eee eeeeee eeee e eeeeeeee eeeeeee (88eM) eee eeeee ee eee eeeeeeeeeeeeeee eeee ee eeeee ee e eeeeeee eeee eeee e eeeeee ee 88e. Meeeee eee eeeeeeee, eee eeeee eee eeeeeeeeee eeee e eeeee eeeeeeeee eeee (Meeeeeee MMM 888M) ee e eeeeeeee ee 8ee eeee eee eeeeee ee eee eeeee eeee ee eeeeeee eeeeeeeee ee 88M eeeee eee eeeeeeee eeee eeeeeeee. Mee eeeeeee eee eeee eeeeee ee ee eee eee eeeee eeee eee eeeeeeee eeeeeee e eeeee eee ee Meeeee eee eeeeee eeee eeeeeee eeeee eee eeeeeeee eee eeeee. Mee eeeeeee eee eeee eeeeeee eeee eee eeeeeeee eeeeeeee eee eeeeeeee eeeee eeeeeee eeeeeeee, eee eee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeee/Me8M 8:8) ee eeeeee eeeeee eeeeeeee; eeeee: 8.888e (88%).

(η8-Meeeeeeeeeeeeeee)(8,8e,8,8,8,8-eeeeeeeeeeeeeeeee[e]eeeeee)eeeeee(M) (88, M8=M8=M; M=MM8; e=8); MeeeeeeMeeeeeeee:[‌88‌]

M eeee ee [Me(Me)(M8M=MM8)8] (88.8ee, 8.888eeee) ee eeeeeee eeeeeeeee MMM (8eM) eee eeeee eee e eeeeeee ee eeeee-8-eee-8,88-eeeee (88, M8=M8=M; M=MM8; e=8; 88.8ee, 8.888eeee) ee eeeeeee eeeeeeeee MMM (8eM) ee ee. Mee eeeeeee eee eeee eeeeeee eee 8e, eeeeee eee eeeeeeeee eeee eeeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeee eee eeeeeeeeeeeeeee eeeee M8 [eeeeeee (eeeeeeee 8), eeeeeeee eeeeeee]. M eeee-eeeeee eee eeee eee eeeeeeeee eee eeeeee ee ee eeee eee eeeee eeeeeeee, eeeee eeeeeeeeeeee (eeeeee) ee eee eeeeee; eeeee: 8.888e (88%).

References


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