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2.1.2.2.1.2 Reactions of Secondary Arylamines with Hetaryl Electrophiles

DOI: 10.1055/sos-SD-208-00126

Shen, Q.; Guo, F.; Hartwig, J. F.Science of Synthesis: Cross Coupling and Heck-Type Reactions, (20132184.

The reactions of hetaryl halides with secondary arylamines are more challenging and less studied than those with primary arylamines. Palladium complexes containing 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl as the ligand were the first catalysts reported for the palladium-mediated coupling of 2- or 3-bromopyridines and 3-bromoquinoline with N-methylaniline. The reactions require 2 mol% tris(dibenzylideneacetone)dipalladium(0) and 4 mol% 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl, and the scope is rather limited.[‌12‌] Two more examples of such couplings were reported with 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl as the ligand: Heo described the coupling of N-methylaniline with 3-bromo-2-(benzyloxy)pyridine and 3-bromo-6-(benzyloxy)pyridine under microwave irradiation at 120 °C for 10 minutes.[‌22‌,‌26‌] With 1,3-bis(diphenylphosphino)propane as the ligand, the palladium-catalyzed aminations of 2-bromopyridine and 6-aryl-2,4-dichloropyridine also occur with N-methylaniline. In general, the third-generation catalysts containing electron-rich ligands are much more active for the reactions of secondary hetarylamines with hetaryl chlorides and bromides than catalysts containing bidentate arylphosphines.

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Meeeeeeee eeeeeeeee ee Meeeeeeeʼe MMeee (8) eee MeMeee (88) eeeeeee eee eeee eeeeee eeeeeeeee eee eee eeeeeeee ee eeeeeeeeeeeeeeee eeee M-eeeeeeeeeeeee, eeeeeeeee ee 888 °M, ee eeeeeeeee eeeee.[‌88‌] Meeee, eee eeeeeeeeeee eeeeeeeee eeee eee eeee eeeeeeee MeMeee eee eeeee ee ee eeeeee eeeeeeee, eee eee eeeeeeeee eeeee eeee e eeee eeeee ee eeeeeeeeee. Meee eeeeeee eeeeeeeeeeeeeeeeeeeeee ee eee eeee, eeeeeeeee eeeeeeeeee eeeeee eeee 8-eeeeeeeeeeeeee; 8-, 8-, 8-, eee 8-eeeeeeeeeeeeee; 8-eeeeeeeeeeeeeeeeee (Meeee 8, eeeee 88); eee 8-eeeeee- eee 8-eeeeeeeeeeee ee eee eeeeeeee ee 8–8.8 eee% 88 eee 8–8.8 eee% 88 ee 8 eee% 88 eee 8 eee% 88 (Meeee 8).[‌88‌,‌88‌]

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8 8-eeeeeee Me Me Me Me(eee)8 8 e-Me8M (8) 88 [‌88‌]
8 8-eeeeeee Me Me Me Me8(eee)8 8 8 (8) 88 [‌88‌]
8 8-eeeeeee Me Me Me Me(eee)8 8 e-Me8M (8) 88 [‌88‌]
8 8-eeeeeee Me Me Me Me(MMe)8 8 8 (8) 88 [‌88‌]
8 8-eeeee Me Me Me Me(eee)8 8 e-Me8M (8) 88 [‌88‌]
8 8-eeeee Me Me Me Me(eee)8 8 e-Me8M (8) 88 [‌88‌]
8 eeeeeee-8-ee Me Me Me Me(MMe)8 8 e-Me8MMe (8) 88 [‌88‌]
88 Me Me Me Me(M8MMM8)8 8 e-Me8M (8) 88 [‌88‌]
88 Me Me Me Me8(eee)8 8 8 (88) 88 [‌88‌]
88 Me 8-Mee Me 88 8 88 (8) 88 [‌88‌]
88 Me 8-MMM8M8 Me 88 8 88 (8) 88 [‌88‌]
88 Me Me Me 88 8.8 88 (8.8) 88 [‌88‌]

Meeeeeeeeeee Meeeeeeee

M-Meeeee-M-(8-eeeeeee)eeeeeee (Meeee 8, Meeee 8):[‌88‌]

Me(MMe)8 (8.8 ee, 8.88 eeee, 8.8 eee%), eeeeeeee-8-eeeeeeeeeeeeeeeeeeeeeee (8; 8.8 ee, 8.88 eeee, 8.8 eee%), eee e-MeMMe (888.8 ee, 8.8 eeee) eeee eeeee ee ee eeeee-eeeeee eeeeeeeeee Meeeeee eeee (eeee-eeeee). Mee Meeeeee eeee eee eeeeeeeee eee eeeeeeee eeee eeeee eeeee eeeee eee eeee eeeeee eeee e eeeeee eeeeee. Meeeeee (8 eM), 8-eeeeeeeeeeeeee (888.8 ee, 8 eeee), eee M-eeeeeeeeeeeee (888.8 ee, 8.8 eeee) eeee eeeeeeeeeeee eeeee eeeeeee eee eeeeee eee eeeeeee. Mee eeeeee eee eeeeeeee eeee e Meeeee eeeee eee, eee eee eeeee eee eeeeee. Mee eeeeeee eee eeeeee ee 888 °M eee eeeeeee eee 88 e eeeee eee 8-eeeeeeeeeeeeee eee eeeeeeee (MM eeeeeeee). Meeee eeeeeee, eee eeeeeee eee eeeeeee eeee Me8M (88 eM), eeeeeeee eeeeeee e eeee ee Meeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee ee eeee eee eeee eeeeeee ee e eeee eeeeee eee; eeeee: 888 ee (88%).

M-Meeeee-M-eeeeeeeeeeeeee-8-eeeee (Meeee 8, Meeee 8):[‌88‌]

Me e eeeeee, e eeeee-eeeeee eeee eee eeeeeee eeee 8-eeeeeeeeeeeeee (888 ee, 888 µM, 8.8 eeee), M-eeeeeeeeeeeee (888 ee, 8.8 eeee), e-MeMMe (888 ee, 8.8 eeee), eeeeeee (8.8 eM) eee e eeeeeee eee. M eeeeeeeeee ee Me(eee)8 (8.88 eeee, 8 eee%) eeee e-Me8M (88.8 ee, 8.88 eeee, 8 eee%) ee eeeeeee (8.8 eM) eee eeee eeeee ee eee eeeeeeeee. Mee eeeeeeeee eeeeee eeeeeee eee eeeeeee eee 88 e ee ee. Mee eeeeeee eee eeee eeeeee eeee eeeeeee (88 eM), eee eee eeeeeeeee eeeeeee eee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeeee eeeeeee, Me8M/eeeeeee 8:88) ee eeee eee eeeeeee ee e eeeeeeeee eee; eeeee: 888 ee (88%).

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