Navigation

0 Hits

  • Previous / Next

You are using Science Of Synthesis as a Guest.
Please login to access the full content or check if you have access via
32.5.3.1.2.1.2 Variation 2: Copper-Catalyzed C—O Bond-Forming Reactions

DOI: 10.1055/sos-SD-032-00627

Milata, V.; Rádl, S.; Voltrová, S.Science of Synthesis, (200832598.

Vinyl bromides or iodides undergo copper-catalyzed coupling with sodium methoxide to give corresponding vinyl ethers.[‌37‌] Moderate yields of vinyl ethers are obtained with complete retention of configuration when the reaction is performed at 110°C in a mixture of methanol and 1-methylpyrrolidin-2-one: this suggests that the reaction is not a simple nucleophilic displacement reaction. Various phenol derivatives undergo similar reactions with vinyl bromides or iodides in the presence of cesium carbonate.[‌38‌] The reaction is efficient with a wide range of di-, tri-, and tetrasubstituted vinyl bromides 22, and is compatible with the presence of electron-donating as well as electron-withdrawing groups on the phenol. The reaction using copper(I) chloride proceeds well in the presence of a range of ligands used in the copper-catalyzed Ullmann diaryl ether synthesis, but good results for enol ethers 23 are sometimes achieved without any ligand. The E/Z stereochemistry of the vinylaryl ether bond corresponds to that of the starting vinyl halide (Scheme 13). On the other hand, geminal alkenyl bromides give a 1:1 mixture of 1- and 2-ethers.

Meeeee 88 Meeeeeee ee Meeeeeeeeee Meeee Meeeeeee eeee Meeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 M8 M8 Meeee (M/M) Meeee (%) Mee
Me Me Me 8-MMe 88 [‌88‌]
Me Me Me 8-Me 88 [‌88‌]
Me Me Me 8-M 88 [‌88‌]
M Me M 8-Me 8:8 88 [‌88‌]
Me M M 8-Me 8:8 88e [‌88‌]
Me Me M 8-MMe 8:8 88 [‌88‌]

e 8:8 eeeeeee ee 8- eee 8-eeeeeeeeeee eeeeee.

Meeeeee eeeeeeee ee eeeee, eeeeeeeee, ee eeeeee eeeeeeee eeee eeeee eeeeeee ee eeeeeeee 88 ee eee eeeeeeee ee 8,88-eeeeeeeeeeeeee-eeeeeee eeeeeee eeeee eeee eeeeee ee eee eeeeeeeeeeeee eeeee eeeeee 88 (Meeeee 88).[‌88‌] Mee eeeeeeee eeeee eee eee eeeeeee eeeee ee eeeeeeee eeee eeeeeeeeeeeee, eeeeeeeee eeeeeeeeee ee eee eeeee eeeeeeeee > eeeeeeeeeeeeeeeeee > eeeeeeee. Mee eeeeeeeeee ee eee eeeeeeee eeeeee eeee eee eeeeeeeeeeeee ee (M)-eeeee eeeeeee eeeee eeeee eeeeeeee eeeeeeeeee, eeeeeeeeee ee e β-eeeeeeeeeee (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeee ee Meeeeeeeeee Meeee Meeeeee eeee Meeeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 M8 M Meeee (%) Mee
(MM8)8Me M (MM8)8Me M 88 [‌88‌]
MMMe M (MM8)8Me M 88 [‌88‌]
Me M (MM8)8Me M 88 [‌88‌]
(M)-MM=MM(MM8)8Me M (MM8)8Me M 88 [‌88‌]
MMMe M (MM8)8Me M 88 [‌88‌]
Me Me Me Me 88 [‌88‌]

Me eee eeee ee eeeeeee eeeeeeee, eee eeeee eeeee eeeeee eeeeee ee eeeeee-eeeeeeeee MM eeee eeeeeeeee eeeeeee e eeeeeee Meeeeee eeeeeeeeeeeee eeeee eee eeeeeeeeee ee eee eeeeeeee ee eeee eeeeeeee ee eeeee eeeee eeeeee, e.e. 88, eee eeeeeee eeeeeeeee, e.e. 88 (Meeeee 88).[‌88‌] Me eeeeeee, ee eeeee eeeeeeeeeeee (e.e., 88 ee 88°M), eee eeeeeeee eeeee eeeeee eee eeeeeeeeeeeee eeeee eeeee eeeee, eeeeeee eeeeeee eee eeeeeeee eeeeeeeeeee eeee 88 ee 888°M eeeee ee ee eeeeeeeee eeeeeee eeeee ee e eeeeeee ee eee eee eeeeeeee. Mee Meeeeee eeeeeeeeeeeee eeeeeee (e 8:8 eeeeeee ee eeeeeeeeeeeee) ee eeeeeeee eeeeee eeeeeeeeeee eeee eee eeeeeeee ee eeeeeeeee ee 888°M.[‌88‌]

Meeeee 88 Meeeeeeee ee ee Meeee Meeee Meeee eee Mee Meeeeee Meeeeeeeeeeee[‌88‌]

Meeeeeeeeee 88

Meeeee Meee (°M) Meeeeeeeee (%) Meeee (%) Mee
88 88
8,88-eeeeeeeeeeeeee 88 88 88 8 [‌88‌]
8,88-eeeeeeeeeeeeee 888 88 88 88 [‌88‌]
8,88-eeeeeeeeeeeeee 888 88 8 88 [‌88‌]
8,8,8,8-eeeeeeeeeee-8,88-eeeeeeeeeeeeee 88 >88 88 8 [‌88‌]
8,8,8,8-eeeeeeeeeee-8,88-eeeeeeeeeeeeee 88 88 88 8 [‌88‌]

M eeee eeeee ee 8-, 8-, eee 8-eeeeeeeeeee eeeeeee eee ee eeeeeeeee ee eeee eeee eeeee eeeeee 88 ee e eeee eee eeeeeeeee eeeeee(MM)-eeeeeeee eeeeeeee eeee eeeeeeeeeeeeeeeeee ee eee eeeeeeee ee eeeeee ee eee eeeeeeeeee eeeee (Meeeee 88).[‌88‌] Meee eeeeee eeeeeeeeeeeeeeeeee eee eeeeeeeeeee eeeeeee eeee eeee eee eeeee eeee eee eeee, ee eeeee 8 eeeeeeeeee ee eee eeeeeee ee eeeeee ee eeeeeee eeeeeeeeee eeeeeeeeeee. Me eeeee 8 eeeeeeeeee ee eee eeeeee(MM) eeeeeeee ee eeee eeeeee. Mee eeee eeeeeee eee eeeeeeee ee eeeee eeeeee(MM) eeeeeee ee eee eeeeeeee: eeeeee eeeeee, eeeeee(MM) eeeeeeee, eeeeee(MM) eeeeeeeeeeeeeeee, eee eeeeee(M) eeeeeee eeee eeeeeeeeeee ee 8, 88, 88, eee 88%, eeeeeeeeeeee. Meeee eeeeeeee eeeeeeeeee eeeeee, eeee ee eeeeee(MM), eeeeeeeee(MM), ee eeeeeee(MM), ee eee eeeeeee eeee eeeeeeee. M eeeeeeeee eeeeeeeee eee eeee eeeeeeee ee eeeeeeee ee Meeeee 88.[‌88‌]

Meeeee 88 Meeeee-Meeeeeee Meeeeeeee ee Meee Meeee Meeeee[‌88‌]

Meeeeeeeeee 88

M8 Meeeeeeeee Meeee (%) Mee
8-Me ee, 88e 88 [‌88‌]
8-Me ee, 88e 88 [‌88‌]
8-Me ee, 88e 88 [‌88‌]
8-M(MM8)8Me ee, 8e 88 [‌88‌]
8-Me ee, 88e 88 [‌88‌]
8-MM 88°M, 88e 88 [‌88‌]
8-MM8 88°M, 88e 88 [‌88‌]
8-MM8Me ee, 88e 88 [‌88‌]
8-MMMe ee, 88e 88 [‌88‌]

Meeeee 88 Meeeeeeee ee eee Meeeee-Meeeeeee Meeeeeeeee ee Meeeeee eeee Meee Meeee Meeeee[‌88‌]

Mee eeeeee ee eeee eeeeeeeeee ee eee eeeeee eeeeeeeeee ee eee eeeeeeeeeeeeeeeee 88 ee eeee eee eeeeeeeeeeeee eee(eeeeeeee)eeeeeeee 88 ee eeeeeeeeeeee eeee eeeeee (Meeeee 88), eeeeeee eee eeeeeeeee eeee eeeeeeeee ee-μ-eeeeeeeee(eeeeeeeee-8,8-eeeee)eeeeeeeee(M)-eeeeeeeee eeeeeeeeeeeeeee eeeeeeee (eee Meeeeee 88.8.8.8.8.8) eeeee eeee eeeeeee.[‌88‌]

Meeeee 88 M Meeeee-Meeeeeee Meeeee Meeeeeeeee[‌88‌]

Meeeeee eeeeee-eeeeeeee eeeee eeeeeeee eeeeeee 8,8-ee-eeee-eeeeeeeeeee eee eeeeeeeeeeee eeeee 88 eeeeeeee eeeeeeee eeeeee ee eee eeeeeeeeeeeee eeeeeeee 88 (Meeeee 88).[‌88‌,‌88‌]

Meeeee 88 Meeeee-Meeeeeee Meeee Meeeeeee eeee e Meeeeeeeeeee Meee[‌88‌,‌88‌]

Meee eeeee eeeeee 88 eee ee eeeeeeeeeee ee eeeee e eeeee-eeeeee eeeeeee 88 ee eeeeeeee eee eeeeeeeeeeeeeee ee e eeeeeeeeeeee eeee eeeeeeeeee.[‌88‌] Mee eeeeee(MM) eeeeeee eeeeeeee eeeeeeee eeeeeeee ee eeeeeeeeeee eeeeeee eeee eeee eeeeeee ee eeeeeeeee ee eeee eeeeeeeeeee ee eee eeeeeeee ee e eeeeeeee eeee (Meeeee 88).[‌88‌] Me eeeee 8 eeeeeeeeee ee ee eeeeeee eeeee eeee ee eeeeeeee ee eeee eee eeeeeee eeee, eee eee eeeeeeeeee eeee eeeeeeee eee ee eeeeeeee ee eeeeee ee eeeeeee eeeee ee ee eeeeeeeee eeee eeee ee eeeeee eeeeeeeee. Mee eeeeeeee ee eeeeeeeeee eeee eee eeeeeeee ee eeee eeeeeeee-eeeeeeeeeee eee eeeeeeee-eeeeeeee eeeeee, eeeeee eeee eeeeeeeeeee eee eeee eeeeee ee eeeeeeee. Meeeee eeeeeeeee ee eeeee-eeeeeeeeeee eeeeeee eeee eee eeeeeeeeeeeee eeeeee eee eeeeeeee eeee 8-eeeee-, 8-eeeeeee-, ee 8-eeeeeeeeeeee. Me eee eeee ee eeeee ee eeee-eeeeeeeeeee eeeeeee, ee eeeeeeee ee eee eeeeeeeeeeeee eeeee-eeeeeeee eeeeeeee eee eeeeeeee.[‌88‌]

Meeeee 88 Meeeeeeeee ee Meeeeee ee MeeeeeeeeeeeeeeMeeeeeee Meeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

8-Meeeeee-8-[(eeeeeeeeeeeeee)eee]eeeeeee (88, M8=M8=M8=Me; M8=8-MMe); Meeeeee Meeeeeeee:[‌88‌]

M eeeeeee ee 8-eeeee-8,8,8-eeeeeeeeeeeeeee (8.8 eeeee), 8-eeeeeeeeeeeee (8.8 eeeee), MeMe (8.88 eeeee), Me8MM8 (8.8 eeeee), 8-[8-(8-eeeeeeeeeeeeee)eeeee]eeeeeeeeee (8.88 eeeee), eee eeeeeee (8.8eM·eeee8) eee eeeeeeee eeeee eee eeeee eeeeee eee eeeeeeeeee eeeeeeee (MMMM). Mee eeeeeee eee eeee eeeeeee eeee e-MeMMe eee eeeeeeee eeeeeee e eeee ee Meeeee. Mee eeeeeeee eee eeeeee eeee 88% ee MM8MM eee eeeee (M8MM8). Mee eeeee eeeeeee eee eeeeeeee ee Meeeeeeee eeeeeeeeeeee eeeee eeee eeeeee; eeeee: 88%.

(8M)-8-(Meeeeeeee)eee-8-eee [88, M8=(MM8)8Me; M8=M; M8=(MM8)8Me]; Meeeeee Meeeeeeee:[‌88‌]

M eeeee-eeeeee eeee eeee eee eeeeeee eeee eeeeee-8-ee (8.8eeee), MeM (88.8ee, 8.8eeee), 8,8,8,8-eeeeeeeeeee-8,88-eeeeeeeeeeeeee (88.8ee, 8.888eeee), (8M)-8-eeeeeee-8-eee (888ee, 8.88eeee), Me8MM8 (888ee, 8.88eeee), eeeeeeee (eeeeeeee eeeeeeee; 888μM, 8.88eeee), eee eeeeeee (888μM). Mee eeee eee eeeeee eeee eee eeeee eee eee eeeeee eeeeeeeeee ee 88°M eee 88e. Mee eeeeeeeee eeeeeeeeee eee eeeeee ee ee eee eeeeeeee eeeeeee e 8×8ee eee ee eeeeee eee, eeeeeee eeee Me8M (888eM). Mee eeeeeeee eee eeeeeeeeeeee eee eee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee [eeeeee eee (8×88ee), eeeeeee eeee eeeeeee/MM8Me8 8:8] ee eeee e eeeeeeeee eee; eeeee: 888ee [88%; eeeee (M/M) >88:8 (MM)].

Meeeeeee-8-ee Meeee Meeee (88, M8=8-Me); Meeeeee Meeeeeeee:[‌88‌]

Meeee Me(MMe)8 (888ee, 8.8eeee) eee eeeee ee e eeee ee eeeeeeee-8-ee (888ee, 8.8eeee) ee MeMM (8eM) ee e eeeee eeeeee eeee e eeeeee. Mee eeeeeee eee eeeeee eeeee eeeeee eee eee M8 eee eeeeeeeeee eeeeeee eee eeeeee eeee e eeeeeee eeeeee eeee e eeeeee. Meeeeeeeeeeeeeeeee (888μM, 8.88eeee) eee eeee eeeee eee eee eeeeeeeee eeeeeee eeeee ee e eeeeeee eeeee. Meeee 88e ee ee, eee eeeeeeeee eeee eeeee eeeeeee eee eeeeee eeee 88% ee MM8MMe (88eM) eee eee eeeeeee eee eeeeeee eee 88eee. Mee eeee, eeeeeee eeeee eee eeeeeeeee eeee MeMMe (8×) eee eee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee eeeee, eeeee (Me8MM8), eee eeeeeeeeeeee. Mee eeeee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (MMMe8/eeeeee 8:8) ee eeee e eeeee eeeee; eeeee: 888ee (88%).

Meeeee 8-Meeeeee-8,8-eee(eeeeeeee)eeeeeeee (88); Meeeeee Meeeeeeee:[‌88‌]

Meeee Me(MMe)8 (88.8e, 88.8eeee) eee eeeee ee e eeee ee eeeeee 8,8-eeeeeeeee-8-eeeeeeeeeeeeeee (8.88e, 88.8eeee) eee MeMM (88eM). Mee eeeeeee eee eeeeee eeeee eeeeee eee eee M8 eee eeeeeeeeee eeee eee eeeeee-eeeeee eeeee eeee e eeeeeee eeeeee eeee e eeeeee. Meeeeeeeeeeeeeeeee (88.8eM, 88.8eeee) eee eeeeee eeeee ee eee eeeeeee, eeeee eee eeeeeee eeeeeeeeee ee ee eeeee M8 eee 88e, eeee eeeeeee eeee MeMMe (888eM), eee eeeeee eeeeeeeeeeee eeee M8M (8×88eM) eee eeeee (88eM). Mee eeeeeee eeeee eee eeeee (Me8MM8), eeeeeeee, eee eeeeeeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, eeeeee/MeMMe 88:8) ee eeee e eeeee eeeee; eeeee: 8.88e (88%); ee 8888°M.

Meeeeeee-8-ee Meeee Meeee (88, M8=8-Me); Meeeeee Meeeeeeee:[‌88‌]

Me(MMe)8 (8.88e 8.88eeee) eee eeeeeee ee ee ee eee MM8Me8 (88eM) eee 88eee. Meeeeeeeeeeeeeeeeeeeeee 8:8 eeeeeee 88 (8.88e, 8.88eeee), eeeeeeee-8-ee (8.88e, 8.88eeee), eee eeeeeeee (8.8eM, 88.8eeee) eeee eeeee, eee eee eeeeeee eee eeeeeee ee ee eee 88e. Mee eeeeeee eee eeeeee eeeeeee e eeeeee (eeeeeee, MM8Me8) ee eeee e eeeee eeeee; eeeee: 8.88e (88%); ee 8888°M.

References


Cookie-Einstellungen