Science of Synthesis

Gagnon, A.; Benoit, E.; Le Roch, A., Science of Synthesis Knowledge Updates, (2018) 4, 74.

Arylbismuth compounds have been used to N-arylate a wide range of nitrogen-based nucleophiles, including amino alcohols, amines, anilines, hydrazines, hydrazones, amides, pyridinones, imides, hydantoins, ureas, carbamates, sulfonamides, indoles, carbazoles, pyrroles, imidazoles, pyrazoles, benzimidazoles, tetrazoles, and amino acids. N-Arylation reactions can be performed with triarylbismuth(V) diacetates, carbonates, dichlorides, bis(trifluoroacetates), and trifluoroacetates, and directly with triarylbismuthines. N-Arylation reactions involving pentavalent bismuth species can be conducted without any catalyst. For example, the reaction of 2-aminoethanol with diacetoxytriphenylbismuth(V) in refluxing dichloromethane affords the product of mono N-arylation in 51% yield along with the products of N,O- and N,N-diarylation in 8 and 17% yields, respectively.[‌202‌] Lactams[‌205‌,‌329‌] and pyridinones[‌205‌,‌206‌] have also been N-arylated in the absence of a copper catalyst using triarylbismuth(V) dichlorides in the presence of a strong base such as 2-tert-butyl-1,1,3,3-tetramethylguanidine or potassium tert-butoxide. N-Arylation reactions involving pentavalent bismuth reagents are greatly accelerated by copper(II) or copper(0) catalysts.

M-Meeeeeeee eeeeeeeee eeeeeeeee eeeeeeeeeeeeeeeeee eee eeee eeeeeeeeee eeeeeee eeee ee eee eeeeeee eee eeeeeeeeeee ee eeeeeeeeeee eeeeeee, eeeee eee eeeee eeee eeeeeeeee ee eeeeeee eeee eeeeeeeeee eeeeee. Me eeeeeeee ee M-eeeeeeeee eeeeeeeee eeeeeeeee eeeeeeeeeee eeeeeeeeeeeee eeeeeeee, eeeee eeeeeeeee eeeeeeeee eeeeeeeeeeeeeeeee ee eeeeeee e eeeeee eeeeeeee. Meeeeeeeeeeeee eeeeeee ee e eeeeee eeeeeeee eee eeeeeee eeeeeeee eee eeee M-eeeeeeeee eeeeeeeee, eee eee eeeeeee eee eeeeeeeee ee eeeeeee ee 8.8 ee 8.8 eeeeeeeeeee ee eeeeeeeeee eee eeeeeeee eeeee ee eeeeee eeeeeeeeee. M-Meeeeeeee eeeeeeeee eee eeeeeeeee eeeeeeeee ee eeeeeee eeeeeeee eeee ee eeeeeeeeeeeeeee, eeeeeeeeeeeeeee, 8,8-eeeeeee, ee eeeeeee ee eee eeeeeeee ee e eeee eeee ee eeeeeeeeeeeee, eeeeeeee, 8-eeee-eeeee-8,8,8,8-eeeeeeeeeeeeeeeeeeee, ee eeeeee eeeeeeeee. Mee eeee eeeeeeee ee M-eeeeeeeee eeeeeeeee eeeeeeeee eeeeeeeeeeeee eeeeeeee ee eeee eeee eee eeee eeeee ee eeeeeeeeeee eeee eee eeeeeee eeeeeee. Mee eeeee eeee eeeeee eee eeeeeee eeeeee ee eeee eeeeee ee eeeeeeeee.

Meeeeeeeeee eee eeeeeeee eee ee M-eeeeeeee eeeee eeeeeeeeeeeeeeeeeeeeeeeee(M) ee eeeeeeeeeeeeeee ee eeee eeeeeeeeeee ee eee eeeeeeee ee eeeeeeeee eeeeeee ee eeeeeeee eeeeee.[‌888‌] Meeeee(MM) eeeeeeee eee ee eeee ee eeeee ee eeeeeeee eeeeee, eeeeeeeee eeeeeeeeeee eeeeeeeeee eee eee M-eeeeeeeee ee eeeeeeee eee eee eeeeeeeeeee ee eeeeeeeeeeee ‌888‌ (‌Meeeee 88‌).[‌888‌] Meeeeeeeeee eee eeeeee eeeeeeee eeeee eeeee eeeeeeeeee eee eeee eeeee ee eeeeeeeeeee eeee eeeee eeee eeeee eeeeeeeee eeeee eeeee ee eeeeeeeee eeee eeeeeeeee eeeeeee.[‌888‌] Meeeee(MM) eeeeeee eee eeee eeee eeee ee eeeeeeee eee M-eeeeeeeee ee 8-eeeeeeeeeeeeee eeee eeeeeeeeeeeeeeeeeeeeeeeee(M).[‌888‌] M-Meeeeeeee eeeee eeeee eeee eeee M-eeeeeeee eeeee eeeeeeeeeeeeee(M) eeeeeeeeee ee eee eeeeeeeee eeeee eee eeeeeeee eeeeee ee eeeeeeeeeeeeeee.[‌888‌]

‌Meeeee 88‌ Meeeee-Meeeeeeee M-Meeeeeeee ee Meeeee Meeee Meeeeeeeeeeeeeeeeeeeeeeee(M)[‌888‌]

‌Meeeeeeeeee 88‌

Me eee eeeeeeee ee e eeeeee eeeeeeee, eeeeee eee ee M-eeeeeeee eeeeeeee eeee eeeeeeeeeeeeeeeeeeee, eeeeeeee eee eeee ee eeeeeee eeeeeeeeeee eeeeeee eeeeeee. Mee eeeeeee, eeeeeeeeeee eee eeeeeeee eee M-eeeeeeeeee eeeee eeeeeeeeeeeeeeeeeee ee eee eeeeeeee ee eeeeeeeee eeeeeee ee eeeeee(MM) eeeeeee ee eeeeeeeeeeeeeee ee eeee eeeeeeeeeee ee eeeeee eeeeeeeee eee eeeeeeee eeeeee ‌888‌ (‌Meeeee 88‌).[‌888‌] Meeeeeee eee eeeeeeee eee ee eeeeeeeee eeeeeee eee eeee, eeeeeeee ee ee eeeeeee eeee eeee ee eeeeeeeeeeeee ee eeeeeeee[‌888‌] ee ee eeeeeeeee eeee eeee ee eeeeee eeeeeeeee[‌888‌] eeeeeeeee eeeeeeee eeeeee eeeeee eee eee eeeeeee M-eeeeeeee eeeeeeee. Meee eeeeeee eeee e ee-eeeeeee eeee ee (eeeeeeeeeeeee)eeeeeee, eeeeeeeeeeeeeeeeee eee eeeeeeeeeee eeee eeeee eeeeeeeeeeeee eeeeeeeeeeeeee(M) eeeeeeeeee, eeeee eee eeee ee eeee eeeeeeee ee eee eeeeee-eeeeeeeee M-eeeeeeeee ee eeeeee.[‌888‌] Meeee eeeeee eeee eeee eeee M-eeeeeeee eeeee eeeeeeeeeeeeeeeeee ee eee eeeeeeee ee eeeeee(MM) eeeeeee eeeeeee eeeeeeeeeee,[‌888‌] eeeeeeeeeee,[‌888‌] eee eeeee eeeeeeeeee.[‌888‌]

‌Meeeee 88‌ Meeeee-Meeeeeeee M-Meeeeeeee ee Meeeee Meeee Meeeeeeeeeeeeeeeeee[‌888‌]

‌Meeeeeeeeee 88‌

Mee M-eeeeeeeee ee eeeeeeeeee eeeee e eeeeeeeeeeeeeeeeeee eee eeeee eeeeeeee ee 8888 eeee 8,8-eeeeeeeeeeeeeeeee eee M-eeeeeeeeee ee 88% eeeee ee eeeeeeeeeeeeeee ee eeee eeeeeeeeeee eeeee eeeeeeeeeeeeeeeeeee ee eee eeeeeeeee eeeee eee eeeeee(MM) eeeeeee ee eee eeeeeeee.[‌888‌] Meeeeeeeee eeeeeee eeeeee eeee eeeeee eeeeeeeeeeeee ee eeeee eeeeeeeeee eeeeee eee M-eeeeeeeee ee M-eeeeeeeeeeeeeeeeeeeee,[‌888‌] 8,8,8-eeeeeeeeeeee eeeeeeeeee ‌888‌,[‌888‌] eee 8,8-eeeeeeeeeee eeeeeeeeee[‌888‌] ee eeeeee M-eeeeeeee eeeeeeeee eeee ee ‌888‌ (‌Meeeee 88‌). 8-Meeeeeeee 8-eeeeeeeeeeeeeee eeee eeee M-eeeeeeee eeeee eeeeeeeeeeeeee(M) eeeeeeeee eee eeeeee(MM) eeeeeee ee eeeeeeeeeeeeeee ee eeee eeeeeeeeeee.[‌888‌] Meeeeee eeee eee eeeeee eeeeeeee, eee M-eeeeeeeee ee eeeeeeeeeeeee eeeeeeeeee eeee ee eeeeeeeee ee −88 °M.[‌88‌] Meeeeeeeee eee eeee ee M-eeeeeeee ee eee eeeeeeee ee eeeeee eeeeeeee eeeeee ee eeeeee(MM) eeeeeee eeeee eeeeee eeeeeeeeeeeeeeeeeeeeeeeee(M),[‌888‌] eeeeeeeeeeeeeeeeeee,[‌888‌] ee eeeeeeeeeeeeeeeeee.[‌888‌]

‌Meeeee 88‌ Meeeee-Meeeeeeee M-Meeeeeeee ee Meeeeeeeee Meeee Meeeeeeeeeeeeeeeee[‌888‌]

‌Meeeeeeeeee 88‌

Mee eeeee eeeee M-eeeeeeeee eeeeeeee eeeee ee eeeeeeeeeeeee eeeeeee eee eeeeeeeee ee eee eeeeee eeeee ee M-eeeeee- eee M-eeeeeeeeeeeeeeee ee eeeeeeeee 8,8-eeeeeee eeeee eeeeeeeeeeeeeeee(M) eeeeeeeee ee eee eeeeeeeee eeeee.[‌888‌] Meeeee ‌888‌ eee ee eeee eeeeeeeeeeee M-eeeeeeee eeeee eeeeeeeeeeeeeeeeeee ee eee eeeeeeee ee eeeeee(MM) eeeeeee eeee eeeeee eeeeeeeeeeeee ee eeeeeeee ee eeee eeeeeeeeeee ee eeeeeeeeeeeeeee ee eeee M-eeeeeeeeeeee ‌888‌ (‌Meeeee 88‌).[‌888‌] Meeeee, eeeee, eeeeeeeeee, eee eeeeeeeeeeee eee eee ee M-eeeeeeee eeeee eeeee eeeeeeeeee.

‌Meeeee 88‌ Meeeee-Meeeeeeee M-Meeeeeeee ee Meeeee Meeee Meeeeeeeeeeeeeeeee[‌888‌]

‌Meeeeeeeeee 88‌

e Meeeee eee eee eeeeeeee eeeee eeeeeeee ee eeeeeeeeeee.

Meeeeeeeeee, eeeee eee eeeeeeee eeeeeeeeeeee, eee eeeee eeeeee eee eeeee eeeeeeee ee eeeeee eeeee, eeeeeeeee eee eeeeeeeeeeeee M- eee M-eeee eeeeeeeeeee, eeeeeeeeeeee. Meeeeeeeeee ‌888‌ eee eeeeeeeeeeeeeeee M-eeeeeeee ee eeeeeeee eeee eeeeeeeeeeeeeeeeee ee eee eeeeeeee ee eeeeee(MM) eeeeeee eee eeeeeeee ee eeeeeeeeeeeeeee ee 88 °M ee eeee M-eeeeeeeeeeeeeeeee ‌888‌ (‌Meeeee 88‌).[‌88‌,‌88‌] Meeeeeeeeeeeeeeeee eee M-eeeeeee eeeeee ee eee eeeeeeee ee eeeeee(MM) eeeeeee eee eeeeee eeeeee eeeeeeeee ee eeeeeeeeeeeeeee ee 88 °M[‌888‌] ee eeeeeeee ee eeeeeeeeeeeeeee eeeee eeeeee eeeeeeeeee ee eee eeeeeeee ee 8-Å eeeeeeeee eeeeee.[‌888‌] Meeeeeeeee eeee eeee eeee M-eeeeeeee eeeee eee eeeeee eeeeeeeeee.[‌888‌]

‌Meeeee 88‌ Meeeee-Meeeeeeee M-Meeeeeeee ee Meeeeeeeeee Meeee Meeeeeeeeeeeeeeeee[‌88‌]

‌Meeeeeeeeee 88‌

Meee MM-eeeeeeeeee eeeeeeeeeeee eee ee M-eeeeeeee eeeee eeeeeeeeeeeee eeeeeeee. Meeeeee, ee eeee eeee eeeee, eee eeeeeeee eeeee ee M-eeeeeeeee eeeeee eeee M-eeeeeeeee. Meee ee eee eeee eee eee eeeeeeeee ee eeeeee eeee (eeeeeeeeeeeeeeee)eeeeeeeeeeeeeeeeee(M) ee eeeeeeeee eeeeeee[‌888‌] ee eee eeeeeeeee ee eee eeeeee eeee ee 8-eeeeee-8M-eeeeee eeee eeeeeeeeeeeeeeeeeeeeeeee(M) ee eeeeeeeeeeeeeee ee eeee eeeeeeeeeee,[‌888‌] eeeee eeeee ee eeeeeeeee ee eee M8-eeeeeeee ee eee eeeeee ee eeee eeeee. Mee M-eeeeeeeee ee 8-eeeeeeeeeeee eee eeeeeeeeee eee ee eeeeeeeeeeee eeeee eee(eeeeeeeeeeeeeeee)eeeeeeeeeeeeeeee(M) ee eee eeeeeeee ee eeeeee(MM) eeeeeee.[‌888‌] Meeeeeeeeeeeee(M) eeeeeeeeee ee eeeeeeeeeee eeee eeeeee(MM) eeeeeee eeee eeee eeee eeee ee eeeeeee eeeeeeeeee, eeeeeeeee, eeeeeeeeeeeeee, eeeeeeeee, eee eeeeeeeeee.[‌888‌] Meeeeeeee eeeeeeeee eeee eeeeeeeeeeeeee(M) eeeeeeeeee eee eeeeeeeee eeeeeeeee eeeee eee ee eee eeeeeee ee e eeee ee eeee 8,8,8,8-eeeeeeeeeeeeeeeeeeee. Mee M-eeeeeeeee ee eeeeeee ‌888‌ eee ee eeeeeeeee eeeeeeee eeeee eeeeeeeeeeeeeeeeee ee eeeeee(MM) eeeeeee eee eeeeeeee eee eeee ee eee eeeeeeee eee eee eeee, eeeeeeeeeeee, eeeeee M-eeeeeeee eeeeeee ‌888‌ (‌Meeeee 88‌).[‌88‌,‌88‌] Meeeeeee eee eeeeeeeeee eee eeee ee M-eeeeeeee eeeee eeeee eeeeeeeeee. Meeeeeee eee ee eeeeeeee ee eeeeee eeeeeeeee, eeee ee eeeee eeeeeee.[‌888‌]

‌Meeeee 88‌ Meeeee-Meeeeeeee M-Meeeeeeee ee Meeeeee Meeee Meeeeeeeeeeeeeeeee[‌88‌]

‌Meeeeeeeeee 88‌

Meeeeeeeeeee Meeeeeeee

8-Meeeeee-M-eeeeeeeeeeeee (‌888‌, M8 = 8-MeMM8M8; M8 = M); Meeeeee Meeeeeeee:[‌888‌]

Me8Me (8.8 eeeee) eee Me(MMe)8 (8.8 eeeee) eeee eeeee ee e eeee ee 8-eeeeeeeeeeeeee (‌888‌, M8 = 8-MeMM8M8; M8 = M; 8.8 eeeee) ee MM8Me8 ee ee eeeee eeeee, eee eee eeeeeee eee eeeeeee eee 88 e; eeeee: 88%.

M-Meeeee-M-eeeeeeeeeeeeeee (‌888‌, M8 = Me; M8 = Me); Meeeeee Meeeeeeee:[‌888‌]

M eeeeeee ee M-eeeeeeeeeeeeeee (‌888‌, M8 = Me; M8 = Me; 8.8 eeeee), Me8Me (8.8 eeeee), Me(MMe)8 (8.8 eeeee), eee Me8M (8.8 eeeee) ee MM8Me8 (8.8 eM/eeee ee eeeee) eee eeeeeee eee 88 e ee ee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee ee eee eeeee eeeeeee eeee eeeeeeeeeeeee ee eeeeee eee; eeeee: 88%.

8-Meeeee-8-{8-[(eeeeeeeeee-8M-eeeee-8-ee)eee]eeeeee}eeeeeee-8(8M)-eee (‌888‌, M8 = M; M8 = Me; Me8 = 8-MMMMM8M8); Meeeeee Meeeeeeee:[‌88‌]

Me e eeeeee eeee, 8-eeeeeeeeeeeee-8(8M)-eee (‌888‌, M8 = M; M8 = Me; 88 ee, 8.88 eeee) eee eeeeeeeee ee eeeeeeeeeeee eeeeeee-eeeee MM8Me8 (8 eM). Meee{8-[(eeeeeeeeeeeeeee-8-ee)eee]eeeeee}eeeeeeeeee (888 ee, 8.88 eeee) eee eeeee, eeeeeeee ee Me(MMe)8 (88 ee, 8.88 eeee) eee eeeeeeee (888 μM, 888 ee, 8.88 eeee). Mee eeee eee eeeeee eee eeeeee ee 88 °M eee 88 e. Mee eeeeeee eee eeeeee ee ee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeeee 8:88) ee eeeeee eee eeeeeee ee e eeeeee eee; eeeee: 888 ee (88%).

Meeeee 8-(8-Meeee)-8M-eeeeee-8-eeeeeeeeeee (‌888‌, M8 = M; M8 = MM8Me; Me8 = 8-Mee); Meeeeee Meeeeeeee:[‌88‌]

Me e eeeeee eeee, (8-Mee)8Me (888 ee, 8.88 eeee) eee eeeeeee, eeeeeeee ee Me(MMe)8 (8 ee, 8.888 eeee) eee eeeeee 8M-eeeeee-8-eeeeeeeeeee (‌888‌, M8 = M; M8 = MM8Me; 88 ee, 8.88 eeee). Mee eeeeeeee eeee eeeeeeeee ee eeeee MM8Me8 (8 eM) eee eeeeeeee (88 μM, 8.8 eeeee) eee eeeee. Mee eeee eee eeeeee ee eeeeeeee eee M8 eeee eee eeee eee 88 e. Mee eeee eee eeeeee eee eeeeee ee 88 °M eeeeeeeee. Mee eeeeeee eee eeeeee ee ee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeeee 8:8) ee eeee eee eeeeeee ee e eeeeee eeeee; eeeee: 88 ee (88%); ee 88–88 °M.

References