Navigation

0 Hits

  • Previous / Next

You are using Science Of Synthesis as a Guest. Please login or sign up for a free trial to access the full content.
2.7.2.1.3 Chlorination with an Oxidant and a Nucleophilic Chloride Source

DOI: 10.1055/sos-SD-218-00127

Sanford, M. S.; Cook, A.Science of Synthesis: Catalytic Transformations via C—H Activation, (20152195.

The combination of an oxidant and a nucleophilic chloride source can also be used to achieve catalytic, ligand-directed Caryl—H chlorination. The first example of this type of transformation was reported in 2006 and involves the palladium-catalyzed directed Caryl—H chlorination of N-acylanilides 35 using a combination of copper(II) acetate as the oxidant and copper(II) chloride as the chloride source. In this system, N-acetylanilides afford significantly higher yields than N-pivaloylanilides (Scheme 14).[‌20‌] This procedure has the advantage of avoiding the use of strong acids and expensive ligands. However, substrates bearing electron-withdrawing groups (e.g., 35, R1 = Me; R2 = Cl) react in lower yield.

Meeeee 88 Meeeeeeee-Meeeeeeee, Meeeee-Meeeeeee Meeee—M Meeeeeeeeeee ee Meeeeeee eeee Meeeee(MM) Meeeeee/Meeeee(MM) Meeeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 Meeee (%) Mee
Me M 88 [‌88‌]
e-Me M 88 [‌88‌]
Me Me 88 [‌88‌]
Me Me 88 [‌88‌]

Me 8888, eeee eeeeeeeee eee eeeeeeee ee eeee eeeeeeeee eee eeeeeeeee eeeeeeeeee [88, M = MMMMMe8 eee M = MMM(eMe)8, eeeeeeeeeeee] (Meeeee 88).[‌88‌] Meeee eeeeeeeee eee eeeeeee eee eeeeeee-eeee, eee eee eeeeeeee eee eeeeee eeeeee eeeeeeee eeeeee eeeeeee. Meeee eeeee eeeeeeeeee, eee eeeeeeee eee ee eeeeee ee 888 eeee. Meee eeeeeeee-eeee eeeeeeeeeeee (e.e., 88) eeee eeeeeeeeeeee eeee ee eee eeeee eeeee ee eeeeeeee, eeeeeeeeee eeeeeeeee eeee eeeeeeeeeee eee-eeeeeeee eeeeeeeeeeeee eeeeeeee eeeeeeeeeeee.

Meeeee 88 Meeeeee-Meee Meeeeeeee-Meeeeeeee, Meeeee-Meeeeeee Meeee—M Meeeeeeeeeee ee Meeeeeee, Meeeeeeeee, eee Meeeeeeeee eeee Meeeee(MM) Meeeeee/Meeeee(MM) Meeeeeee[‌88‌]

Meeeeeeeeee 88

M M8 Meeee (%) Mee
MMMe M 88 [‌88‌]
MMMMe-Me M 88 [‌88‌]
MMMMMe8 MMe 88 [‌88‌]
MMM(eMe)8 M 88 [‌88‌]

Mee eeeeeeeee(MM) eeeeeee eeeeeeeee eeeeeeeeeeee ee 8-eeeeeeeeeeeeeee 88 eee eeee eeeeeeee eeeee e eeeeeee eeeeeeeee eeeeeeeee eeeeee(MM) eeeeeeeeeeeeeeee ee eee eeeeeee ee eeeeee eeee eeeee eee, eeee eeeeeee eeeeeeee ee eee eeeeeeee eeeeee.[‌88‌] Meeee eeeeeeeeee eee eeeeeeeeee eeee eeee eeeeeeee-eeeeeeee (e.e., MMe, Me) eee eeeeeeee-eeeeeeeeeee (e.e., MM8, MM8) eeeeeeeeeeee ee eee eeeeeeee eeee (Meeeee 88).

Meeeee 88 Meeeeeeee-Meeeeeeee, Meeeee-Meeeeeee Meeee—M Meeeeeeeeeee ee 8-Meeeeeeeeeeeeee eeee Meeeee(MM) Meeeeeeeeeeeeeee/Meeeeee Meeeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 Meeee (%) Mee
MMe M 88 [‌88‌]
Me M 88 [‌88‌]
MM8 M 88 [‌88‌]
M MM8 88 [‌88‌]

Meeeee(MM) eeeeeeee eee eeee eeee ee e eeeeeeee eee eee Meeee—M eeeeeeeeeeee ee 8-eeeeeeeeeeee eeeeeeeeeee ee eee eeeeeeee ee eeeeeeeee eeeeee ee eee eeeeeee eee 8,8,8,8-eeeeeeeeeeeeeeeee ee eee eeeeeeee eeeeee ee eeeeeeee (Meeee 8).[‌88‌] Meeee eee eeeeeeee eeeeeeeeee, 8,8,8,8-eeeeeeeeeeeeeeeee eeeee eeeeeeeeeeee eeee, eeeee ee eeeeeeee ee eeeee ee eee eeeeeeeeeeee eeeee. Meeeeeeeeee eeeeeeeeeeeeee ee eee eeeeeeeeee ee eeeeeeee (eeeee 8). Meeeeee, eeeeeeee eee eeeeeeeeeee eeeeeeeee eeeeeeeeeeeeee (eeeee 8). Me ee eeee eeeee eeee eeeeeeee-eeeeeeeee eeeeeeeeee eeeeee eeeee eeeeee (eeeee 8).

Meeee 8 Meeeee-Meeeeeeee, Meeeee-Meeeeeee Meeee—M Meeeeeeeeeee ee 8-Meeeeeeeeeeee eeee 8,8,8,8-Meeeeeeeeeeeeeeee/Meeeee[‌88‌]

Meeee Meeeeeee Meeeeeee Meee (°M) Meeeeee Meeee (%) Mee
8 888 88 [‌88‌]
8 888 88 [‌88‌]
8 888 88 [‌88‌]
8 888 88 [‌88‌]

Me e eeeeeee eeeeeeeeeeeeee, eeeeee eee eeee eeee ee eee eeeeeee eeee eeeeeee eeeeeeee ee eee eeeeeeee eeeeee eee eee eeeeee-eeeeeeeee Meeee—M eeeeeeeeeeee ee 8-eeeeeeeeeeeee (Meeee 8).[‌88‌] Meee eeeeeeeeeeeeee eeeeeeee eeeeee(MM) eeeeeee eeeeeeeeee ee eee eeeeeeee, eee ee eeeeeee eee ee eeeeee eeee ee 888 °M. Me ee eee eeee eeeee ee Meeee 8, eeeeeeeeeeeeee ee eeeee eeeeeeee eeee eeeeeeeeee eeee eeee eee eeeeeeeeee eeeeeeeeee Meeee—M eeeee. Meeeeeee-eeeeeeee eee eeeeeeee-eeeeeeeeeee eeeeee eee eeee eeee eeeeeeeee ee eeee eeeeeeeeeeeeee (eeeeeee 8 eee 8, eeeeeeeeeeee).

Meeee 8 Meeeee-Meeeeeeee, Meeeee-Meeeeeee Meeee—M Meeeeeeeeeee ee 8-Meeeeeeeeeeee eeee Meeeeee Meeeeeee/Meeeee[‌88‌]

Meeee Meeeeeee Meeeeeee Meeeeee(e) Meeee (%) Mee
8 88 [‌88‌]
8 88 [‌88‌]
8 88 [‌88‌]
8 88 [‌88‌]

Meeeeeeeeeee Meeeeeeee

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

Me e eeeee Meeeeee eeee eeee eeeee M-eeeeeeeeeeeeeee (88, M8 = Me; M8 = M; 8.8 eeee, 8 eeeee), Me(MMe)8 (8.88 eeee, 8.8 eeeee), MeMe8 (8.8 eeee, 8 eeeee), eee Me(MMe)8 (8.8 eeee, 8 eeeee). Mee eeee eee eeeeee eeee e eeeeee eeeeee, eeeeeeeee, eee eeeeeeee eeee M8 (8 ×). 8,8-Meeeeeeeeeeeee (8 eM) eee eeeee eee eeeeeee eee eeee eee eeeeeee eee eeeeee ee 88 °M ee ee eee eeee eee 88 e. Mee eeeee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeeeee eeeee/MeMMe); eeeee: 88%.

M-(8-Meeeeeeeeeee)eeeeeeeee (88, M = MMMe; M8 = M); Meeeeee Meeeeeeee:[‌88‌]

M-Meeeeeeeeeeeeee (88, M = MMMe; M8 = M; 8.8 eeee, 8 eeeee), MeMe8 (888 ee, 8.8 eeee, 8 eeeee), Me(MMe)8 (888 ee, 8.8 eeee, 8 eeeee), eee Me(MMe)8 (8.88 eeee, 8.88 eeeee) eeee eeeee ee e eeeeee eee eeeeee eeee e eeeeee, eeeeeee e eeeeeeeeeee eeeeee. Mee eeeeeee eee eeee eeeeeeeeeee ee e eeeee-eeeeee eeeee eeee, eeeee eee eeeeee ee 888 °M eee 88 e eeeeeee eeeeeeee. Meeee eeeeeee ee ee, eee eeeeeee eee eeeeeee eeee e eeeeeee eee eeee eeeeeeee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeee/MeMMe); eeeee: 88%.

8-(8-Meeeee-8-eeeeeeeeeeeee)eeeeeeeeee (88, M8 = MMe; M8 = M); Meeeeee Meeeeeeee:[‌88‌]

8-(8-Meeeeeeeeeeee)eeeeeeeeee (88, M8 = MMe; M8 = M; 8 eeeee), Me(MMe)8 (8.88 eeeee), Me(MMMMM8)8 (8.8–8.8 eeeee), MeMe8 (8.8–8.8 eeeee), eee MeMM/Me8M (8.8:8) eeee eeeee ee e 88-eM eeeee. Mee eeeeeee eee eeeeee ee 888 °M eee 8.8 e. Mee eeeeeee eee eeee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Me MeMMM8 (88 eM) eee eeeee ee eee eeeeeee, eee eeee eeeeeee eee eeeeeeeee eeee MeMMe (8 × 88 eM) eee eee eeeeeeee eeee eeeeee eeee eeeee. Mee eeeeeee eeeee eee eeeee (Me8MM8) eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeee eeeeeee eee eeee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeeeee eeeee/MeMMe); eeeee: 88%.

8-[8-Meeeee-8-(eeeeeeeeeeeeeee)eeeeee]eeeeeeee (Meeee 8, Meeee 8); Meeeeee Meeeeeeee:[‌88‌]

8-[8-(Meeeeeeeeeeeeee)eeeeee]eeeeeeee (8.8 eeee, 8 eeeee), MeMe8 (8.8 ee, 8.88 eeee, 8.8 eeeee), eee 8,8,8,8-eeeeeeeeeeeeeeeee (8 eM) eeee eeeee ee e 88-eM eeee, eeeee eee eeeeee eeeee M8. Mee eeee eee eeeeee eee eeeeee ee 888 °M eee 88 e. Mee eeeeeeeee eeeeeee eee eeee eeeeeee eeee MM8Me8 (88 eM) eee eeeeeeee eeee ee Me8M (88 eM). Meee eeeeeee eee eeeeeeee eeeeeee Meeeee, eee eee eeeeeeee eee eeeeee eeee eeeee (8 ×). Mee eeeeeee eeeee eee eeeee (Me8MM8) eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeee/Me8M); eeeee: 88%.

8-(8-eeee-Meeee-8,8-eeeeeeeeeeeeee)eeeeeeee (Meeee 8, Meeee 8); Meeeeee Meeeeeeee:[‌88‌]

8-(8-eeee-Meeeeeeeeee)eeeeeeee (8.8 eeee, 8 eeeee), MeMe (8.8 eeee, 8 eeeee), Me(MM8)8•8M8M (88 ee, 8.88 eeee, 8.8 eeeee), eee MeMM (8 eM) eeee eeeeee eeeee M8 ee e 88-eM eeee, eeeee eee eeee eeeeee eee eeeeee ee 888 °M. Meee eeeeeeee eeeeeeeeee, ee eeeeeeeeee ee MMM, eee eeeeeeee eee eeeeeeee eeee eee. ee MeMMM8 eee eeeeeeeee eeee MeMMe (8 × 88 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee eeeee (8 × 88 eM), eeeee (Me8MM8), eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeeeee eeeee/Me8M 8:8); eeeee: 88%.

References