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4.3.15.2.1.2 O-Arylation Reactions

DOI: 10.1055/sos-SD-104-00490

Gagnon, A.; Benoit, E.; Le Roch, A.Science of Synthesis Knowledge Updates, (2018469.

Arylbismuth compounds are effective reagents for the O-arylation of alcohols, phenols, and other oxygen nucleophiles. Depending on the reaction conditions, carbonyl compounds and phenols can be C-arylated (see Section 4.3.15.2.1.1) or O-arylated. The O-arylation of 5,5-dimethylcyclohexane-1,3-dione was accomplished using bis(trifluoroacetoxy)triphenylbismuth(V) in the presence of 10 mol% metallic copper[‌314‌] or (trifluoroacetoxy)tetraphenylbismuth(V) in the presence of 0.6 equivalents of trichloroacetic acid.[‌311‌] The O-arylation of ethyl 2-oxocyclohexane-1-carboxylate using (trifluoroacetoxy)tetraphenylbismuth(V) has been realized, but trichloroacetic acid had to be replaced by 2-tert-butyl-1,1,3,3-tetramethylguanidine for optimal yields.[‌311‌]

8,8-Meeee 888 (eee 8,8-eeeee) eee ee eeeeeeeeeeeeee ee eeeeeeeeeeeeeeeeeeeeeeeee(M) ee eeeeeeeee eeeeeeeeeeeeeee ee eeeeeee eeeeeee eeeeee 888 (Meeeee 88).[‌888‌,‌888‌]

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

Meeeeeeeeee 88

M8 M8 Meeee (%) Mee
M M 88 [‌888‌]
Me Me 88 [‌888‌]
(MM8)8 88e [‌888‌]
(MM8)8 88e [‌888‌]

e Mee eeeeeeeee ee eeeee-eeeeeeeeeee-8,8-eeee.

e Mee eeeeeeeee ee eee-eeeeeeeeeee-8,8-eeee.

Me eeeeeeeeeeeeeeee eeeeee-eeeeeeeee eeeeeee eeeeeeeee e eeeeee eeeeeeeeeeeeeeeeee eee eeeeeeeee, eeeeeeeee eeeeeeeeeeeeeee eeeeeeeeeeee eeeee ee eeee eeeeee eee eeeeee eeeeeeeeeeee eeeeeeee.[‌888‌,‌888‌]

Meeeee eeeeeeee eee eee eeeeeeee ee eeeeeeeeeeeeeeeeeeeeeeeee(M) eeeeee ee eeeeeeee-eeeeeeeeeee eeeee ee eeeeeee ee eee eeeeeeee eeeeee, eeee ee ee 8-eeeeeee- ee 8-eeeeeeeeeeeeee.[‌888‌] Meeeeee, eeeeeeeeeee eeeeeeee eee ee eeeeeeeeee eeeee (eeeeeeeeeeeeeeee)eeeeeeeeeeeeeeeeee(M) ee eeeeeeeee eeeeeee.[‌888‌] Meeeeeeeeeeeeeeeeeeeeeee(M) ee eeee e eeeeee eeeeeee eee eee eeeeeeeeeee ee eeeeeeee 888, eeeee eeeeeee eeeeee 888, eeeeeeee eeee eee eeeeeeee ee eeeeeeeee ee eee eeeeeeee ee e eeeeeeeee eeeeee ee eeeeee(MM) eeeeeee ee eeee ee e eeeeeeee eeee eeee ee M,M-eeeeeeeeeeeeeeeeeeeeeee (Meeeee 88).[‌888‌,‌888‌,‌888‌] Meeeeeee eee eeeeeeee eee ee eeeeeeeee ee eeeeeeeeeeeeeee, eeeeeee eeeeeeee e eeeeeee eeeeeeeee eeeee. Meeee eeeeeeeeee eeee eeee ee M-eeeeeee ee eeeeeeeeeeee ee eeeee ee eeeeeeeeeeee M.[‌888‌]

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

Meeeeeeeeee 88

M8 Meeee (%) Mee
e-Me 88 [‌888‌]
MMe8Me 88 [‌888‌]
8-eeeeeeeee eeeee [‌888‌]
Me 88 [‌888‌]
MMe8(MM8)8Me 88 [‌888‌]

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

Mee ee eee eeeeeeee ee ee eeeeeeee-eeeeeeeeeee eeeeeeee eeeee, α-eeeeeee eeeeeeee eeeeeeeee eee eeee eeeeeeee eeee eeeeee eeeeeeeeeeeeeeee eeeeeeee. Mee M-eeeeeeeee ee eeeeeee, ee α-eeeeeee eeeeee eeee eeee eee eeeeee eeeee ee eee α-eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeeeeeeeeeeeeeeeeeeeee(M).[‌888‌] Mee M-eeeeeeeee ee α,α-eeeeeeeeeeeee α-eeeeeee eeeeeeee eeeeeeeee 888, eeeee eee eeee eeeeeeeeeee eeeeeeeeee eee ee eee eeeeee eeeeeeeeee eeeeeee ee eeee eeeeee ee eee α-eeeeeeee, ee eeeeee 888, eee ee eeeeeeeee eeeee eeeeeeeeeeeeeeeeeeeeeeeee(M) ee eeeeeeeee eeeeeee ee eeeeee(MM) eeeeeee eee eeee ee eeeeeeeeeee eeee M,M-eeeeeeeeeeeeeeeeeeeeeee (Meeeee 88).[‌888‌,‌888‌] Meee eeeeeeeeeeeeee eee eeee ee eeeeeeeeeeee eeeee eeeeeeeeeeeeeeeeee(M) eeeeeeeeeeeeeeeee ee eeeeeeeeeeeeeeeeeeeeeeee(M). Mee eeeeeeeeeeee ee eeeeeeeeeee eeee eeeeee ee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeeeeeeeeee(M) eeeeeeeeee ee eee eeeeeeee ee eeeeee(MM) eeeeeee eee M,M-eeeeeeeeeeeeeeeeeeeeeee.[‌888‌] M-Meeeeeeee ee α-eeeeeee eeeeeeee eeeeeeeee eee eeee ee eeeeeeeee eeeeeeee eeee eeeeeeeeeeeeeeeeeee ee e ee-eeeeeee eeee ee (eeeeeeeeeeeee)eeeeeee ee eeeeeee ee eeeeeeeeeee eeee eeeeee(MM) eeeeeee, M,M-eeeeeeeeeeeeeeeeeeeeeee, eee eeeeeeeee eeeeee.[‌888‌]

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

Meeeeeeeeee 88

M8 M8 Meeee (%) Mee
Me Me 88 [‌888‌]
Me Me 88 [‌888‌]
MMe Me 88 [‌888‌]
MMe Me 88 [‌888‌]
eeeeeeeeee-8-ee Me 88 [‌888‌]

Mee ee eee eeeeeeeee eeeeee ee eee eeeee eeeee, 8,8-eeeee eeeeeeee eee eeee eeeeeeee eeeeeeeeee eeee eeeeee eeeeeeee ee M-eeeeeeeee eeeeeeeee eeee eeeeeeeeeeeee eeeeeeee. Meee, eee M-eeeeeeeee ee 8,8-eeeee eeeeeeee 888 ee eeeeeee eee eeeeeeeeeeeee eeeeee 888 eee ee eeeeeeeee eeeee eeeeeeeeeeeeeeeeee ee eee eeeeeeee ee eeeeeeee eee eeeeeeeeeeeeeeeee eeeeeee ee eeeeee(MM) eeeeeee ee eeeeeee ee 88°M eeeee eeeeee (Meeeee 88).[‌888‌] Meee-eeeeeeee eeeeeeeeee eeee ee 8-(eeee-eeeeeeeeeeeeeeeeeee)-8-eeeeeeeeeeeeeeeee (888, M8 = Me; M8 = Mee) eee eeee eeeeeeee eeeee eeeeeeeeeeeeee eeeeeee ee eeeeee(MM) eeeeeee. Meeee eeeeeeeeee eeee eeee ee eeeeeee M-eeee-eeeeeeeeeeeeee eeeeeeeeeeeeeee eeeeeeeeeee.[‌88‌]

Meeeee 88 Meeeee-Meeeeeeee M-Meeeeeeee ee 8,8-Meeee Meeeeeee Meeee Meeeeeeeeeeeeeeeee[‌888‌]

Meeeeeeeeee 88

M8 M8 Me8 Me(MMe)8 (Meeee) Meeee (%) Mee
Me Mee 8-Mee 8.8 88 [‌888‌]
Me Mee 8-MM8M8 8.8 88 [‌888‌]
Me Mee 8-Mee 8.8 88 [‌888‌]
Me Mee Me 8.8 88 [‌888‌]
Me Mee Me 8 88 [‌888‌]
Me Me Me 8 88 [‌888‌]

Meee eeeeeeeeee eeee eeee eeeeeeee eee eee M-eeeeeeeee ee eeeeeee eeeee eeeeeeeeeeeee eeeeeeee. Meeee eeeeeeeeee eee ee M-eeeeeeee eeeee (eeeeeeeeeeeeeeee)eeeeeeeeeeeeeeeeee(M) ee eeeeeeeee eeeeeee.[‌888‌,‌888‌] Mee eeeeeeeeeeeeee eee eeee ee eeeeeeeee ee eeeeeee ee 88°M ee 8.8 eeeeeeeeeee ee eeeeeeeeeeeeeee eeee eee eeeee,[‌888‌] ee ee eeeeeeeeeeeeeee ee eeee eeeeeeeeeee ee eee eeeeeeee ee 88 eee% ee eeeeee(MM) eeeeeee.[‌888‌] Meeeeeeeeeeeeeeeeeeeeeeee(M) eee eeee ee eeee ee M-eeeeeee eeeeeee ee eeee eeeeeeeeeee, eee eee eeeeeeee eeeeeeee eee eeeeeeee ee 88 eee% ee eeeeeeee eeeeee.[‌888‌] Mee M-eeeeeeeee ee eeeeeee 888 ee eeee eee eeeeeeeeeeeee eeee eeeeee 888 eeeee eeeeeeeee eeeeeeeeeeeee eeeeeeeee (eeeeeee ee eeeeeeeeeee eeeeeeeee) eee ee eeeeeeee ee eee eeeeeeee ee 8.8 eeeeeeeeee ee eeeeee(MM) eeeeeee (Meeeee 88).[‌88‌,‌88‌,‌888‌] Meeeee(MM) eeeeeee eeeeeeee eee ee eeeeeee ee eeeeeeeeeeeeeeeee eeeeeee ee eee eeeeeeee ee eeeeeeeee eeeee eeeeee.

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

Meeeeeeeeee 88

Me8 Me8 Meeee (%) Mee
8-MeMM8M8 8-Mee 88 [‌88‌]
8-MM8M8 8-Mee 88 [‌88‌]
8-MeM8M8 8-Mee 88 [‌88‌]
Me 8-Mee 88 [‌88‌]
8,8-Me8M8M8 8-MM8M8 88 [‌88‌]

8-Meeeeeeeeeeeeee eeee eee eeee eeeeeeee eeeee eeeeeeeeeeeeeeeeee(M)[‌888‌] ee (eeeeeeeeeeeeeeee)eeeeeeeeeeeeeeeeee(M) ee eeee eeeeee 8-eeeee eeeeeee.[‌888‌] Mee M-eeeeeeeee ee eeeeeeee eeeee 888 eee ee eeeeeeeee eeeee 88-eeeeeeeeeeeeeeeeeeee 8,8-eeeeeeee 888 ee eee eeeeeeee ee 8.8 eeeeeeeeeee ee 8-eeeeeeeeeeeeeeeeeee eeee, eeeeeeeee eeeeeeeeee 888 ee ee ee 88% eeeee (Meeeee 88).[‌888‌,‌888‌]

Meeeee 88 M-Meeeeeeee ee Meeeeeee Meeee Meeee Meeeeeeeeeeeeeeeeeee Meeeeeee[‌888‌,‌888‌]

Meeeeeeeeee 88

M8 Me8 Meeee (%) Mee
8-Mee 8-Mee 88 [‌888‌,‌888‌]
8-Mee 8-Mee 88 [‌888‌,‌888‌]
8-Mee 8-MeM8M8 88 [‌888‌,‌888‌]
Mee Me 88 [‌888‌]
Me Me 88 [‌888‌]

Meeeeeeeeeee Meeeeeeee

8-Meeeeeeeeeeeee (888, M8 = M8 = M):[‌888‌]

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

8,8-Meeeeeee-8-eeeeeeeeeeee Meeeee Meeee [888, M8 = MMe8(MM8)8Me]:[‌888‌]

Me(MMe)8 (88 ee, 8.88 eeee, 88 eee%) eee eeeee ee e eeee ee 8-eeeeee-8-eeeeeeeeeee-8-ee [888, M8 = MMe8(MM8)8Me; 88 ee, 8.8 eeee], eee Me8MMe (8.888 eM, 888 ee, 8.8 eeee) ee eeeeeee (8.8 eM). Mee eeeeeee eee eeeeeee ee ee eee 88 eee. Meee, Me8MeM (888 ee, 8.8 eeee) eee eeeee eee eee eeee eee eeeeeee ee ee eee 8 e eeeee eee eeeeeee eeeeeeeee ee eeeeeeee. 8% ee MM8 eee eeeee eee eee eeeeeee eee eeeeeeeee eeee MM8Me8 (eeeee eeeee). Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee eeeee, eeeee (Me8MM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeeeeeeee MMM (eeeeee eee, eeeeeee/MM8Me8 8:8) ee eeeeee eee eeeeeee ee e eeeeeeeee eee; eeeee: 88 ee (88%).

eeee-Meeee (M)-[8-Meeeee-8-(8-eeeeeeee)eeeee]eeeeeeeee (888, M8 = Me; M8 = Mee; Me8 = 8-Mee):[‌888‌]

Me e eeeeee eeee, (8-Mee)8Me (888 ee, 8.88 eeee) eee eeeeeee, eeeeeeee ee Me(MMe)8 (88 ee, 8.88 eeee) eee eeee-eeeee (M)-(8-eeeeeee-8-eeeeeeeeeee)eeeeeeeee (888, M8 = Me; M8 = Mee; Me8 = 8-Mee; 88 ee, 8.88 eeee). Mee eeeeeeee eeee eeeeeeeee ee eeeee eeeeeee (8 eM). Meeeeeee (88 μM, 88 ee, 8.88 eeee) eee eeeee eee eee eeee eee eeeeee eeee eee M8 eee 88 e, eeeeee, eee eeeeee ee 88°M eeeeeeeee. Mee eeeeeee eee eeeeee ee ee eee eeeeeeeeeee eeee e eeeee-eeeeeeee eeeee, eeeeeee eeee MeMMe. Meeeee eee eee eeeee eee eee eeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeeee 8:88) ee eeeeee eee eeeeeee ee e eeeeeeeee eee; eeeee: 88 ee (88%).

8-Meeeeeeeeeee 8-Meeee Meeee (888, Me8 = 8-MM8M8; Me8 = 8-Mee):[‌88‌]

Me e eeeeee eeee, 8-eeeeeeeeeeee (888, Me8 = 8-MM8M8; 88 ee, 8.88 eeee) eee eeeeeeeee ee eeeeeeeeeeee eeeeeee-eeeee MM8Me8 (8 eM). (8-Mee)8Me (888 ee, 8.88 eeee) eee eeeee, eeeeeeee ee Me(MMe)8 (88 ee, 8.88 eeee) eee Me8M (888 μM, 88 ee, 8.88 eeee). Mee eeee eee eeeeee eee eeeeee ee 88°M eee 8 e. Mee eeeeeee eee eeeeee ee ee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeeee 8.8:88.8) ee eeee eee eeeeeee ee e eeeeee eee; eeeee: 88 ee (88%).

References