Science of Synthesis

Gagnon, A.; Benoit, E.; Le Roch, A., Science of Synthesis Knowledge Updates, (2018) 4, 66.

Arylbismuth compounds have been used to arylate carbon nucleophiles. For example, cholestan-3-one (‌134‌) is C-arylated by sequential treatment with potassium hydride and triphenylbismuth(V) carbonate to afford α,α-diphenylated product ‌135‌ (‌Scheme 75‌).[‌307‌] In another example, sequential treatment of cyclohexanone with excess potassium hydride and triphenylbismuth(V) carbonate in tetrahydrofuran gave the corresponding tetraphenyl compound 2,2,6,6-tetraphenylcyclohexanone in 93% yield.[‌308‌] Monophenylation of the benzophenone imine derivative of glycine ethyl ester was also accomplished in good yield using triphenylbismuth(V) carbonate in refluxing dimethylformamide.[‌309‌] A triarylbismuth(V) dichloride species was utilized in combination with 1,8-diazabicyclo[5.4.0]undec-7-ene to arylate an enol intermediate en route to the natural product maoecrystal V.[‌54‌]

‌Meeeee 88‌ M-Meeeeeeee ee Meeeeeeee-8-eee Meeee Meeeeeeeeeeeeeee Meeeeeeee[‌888‌]

Meeeeee eee ee eeeeeeeeee ee eee eeeee eeeeeeee eeeee eeeeeeeeeeeeeeeeee(M) ee eeeeeeeeeeeeeee ee eeeeeee ee eeee eeeeeeeeeee.[‌888‌,‌888‌] Mee eeeeeee, eeeeeeeee ee eeeeeeeeee-8-ee eeee eeeeeeeeeeeeeeeeee(M) eeeeeee 8-eeeeeeeeeeeeeeee-8-ee (‌888‌) ee 88% eeeee (‌Meeeee 88‌). Mee eeeeeeeee ee 8,8-eeeeeeeeeeeeee, eeeee eee ee eeeee MM eeeeeeeee eeeeeeeee eee ee eee eeeeeeee ee eee eeeeee eeeeee, eeeeeee eee eeeeeeeeeeee eeeeeee ee eeeee eeeeeeeee 8-eeeeee-8,8-eeeeeeeeeeeeeeeee-8,8-eeeeeee ee 88% eeeee. Mee eeeee eeeeeeeeeee ee eeeeeeeeee-8-ee ee eeee eeeeeeeeeeee ee 88% eeeee eeeee eeeeeeeeeeeeeeeeee(M) eeeeeee ee eeeeeee ee eeee eeeeeeeeeee ee eee eeeeeeee ee 8-eeee-eeeee-8,8,8,8-eeeeeeeeeeeeeeeeeeee.[‌888‌] Meee eeeeeeeeeeeeee eee ee eeeeeeeee eeeee eee eeee eeeeeeeeee ee 88 °M eeeee eeeeeeeeeeeeeeeeee(M) eeeeeeeeeeeeeeee (88%), 8-eeeeeeeeeeeeeeee (88%), ee eeeeeeeeeeeeeeeeeeeeeeeee (88%), eeeeeeeeeeeeeeeeeeeeeeee(M) (88%),[‌888‌] ee eeeeeeeeeeeeeeee(M) eeeeeeeee (88%)[‌888‌] ee eeee eeeeeeeeeee. Meeeeeeeeeeeeeee(M) eeeeeeeee eee eeee eeee ee eeeeeeeee 8-eeeeeeeeeeee, eeeeeeeee 8-eeeeee-8-eeeeeeeeeeee ee 88% eeeee.[‌888‌] Meeeeeeeeeeeeeeeee(M) eeeeeee, eeeeeeeeeeeeeeee, 8-eeeeeeeeeeeeeeee, eee eeeeeeeeeeeeeeeeeeeeeeeee eeee eeee ee eeeeeeeee eeeee 8-eeeeeeeeeeeeee-8-eeeeeeeeeee ee eee α-eeeeeeee ee eeeeeee ee 88 °M ee eee eeeeeeee ee 8-eeee-eeeee-8,8,8,8-eeeeeeeeeeeeeeeeeeee, eeeeeeeee eeeee 8-eee-8-eeeeeeeeeeeeeeeee-8-eeeeeeeeeee ee 88, 88, 88, eee 88% eeeeee, eeeeeeeeeeee.[‌888‌]

‌Meeeee 88‌ eeeee-Meeeeeeeeee ee Meeeeeeeee-8-ee Meeee Meeeeeeeeeeeeeeeee(M)[‌888‌]

α,β-Meeeeeeeeee eeeeeeee eeeeeeeee eeee ee ‌888‌ eeeeeee eeeeeeeeeeeeee α-eeeeeeeeeee eeee eeeeeeeeeee eeeeeeeeeeeee ee eee eeeeeee eeeeee eeee eeeeeeeeee eeeeeeeee eeee eeeeeee eeeeeeeeeeeeeeee eee eeeeeeeeeeeeeeeeeeeeeeee(M) ee eee eeeeeeee ee eeeeeeeeeeeeeeeeeeee eeeeeeee ee eeee α-eeeeeeeeee eeeeeeee eeeeeeeee eeee ee ‌888‌ (‌Meeeee 88‌).[‌888‌]

‌Meeeee 88‌ Meeeeeeeeeeeee α-Meeeeeeeeee ee ee α,β-Meeeeeeeeee Meeee[‌888‌]

Meeeeeeee ee eeeeee eee eeeeeee eeeee eeee eeeeee eeee ee ‌888‌ eeeeeee eeee eeeeeee eee eeeeee eeee eeeeeeeeeeeeeeeeeeeeeeee(M) ee eeeeeeeeeeeeeee ee eee eeeeeeeeeee eeeeee eee eeeeeeeeeeeee eeeeeeeeeeeeee eeeeeeee eeee ee ‌888‌ ee eeee ee eeeeeeeee eeeeee (‌Meeeee 88‌).[‌888‌] Mee eeeeeeeeeeeeee ee eeeeeeee ee eee eeeeeeee ee eee eeeee eeee eeeee, eee eeeeeeeeeee eeeeeeee eee eee eeeeeeee, eeee eeee ee α-eeeeeeee eeee ee eeeeeee ee eee eeeeeee. Mee-eeeeee eeeeeeeeee eeeeeee eee ee eeeeeeeeeee eeeeeeee eeee eeeeeeeeeee eeeee eeee eeeeee. Meeeee-eeeeeee M-eee eeeeeeeeeee eeeeeeee ee eeeeeeeeeeeeeeeeeeeeeeee(M) eeeeeeee eeee eee eeeeeee eeeeee e eeeeeeeee eeeeeeee eeeeeeeeeee eeeeeeee eeee eeeee eeee eeeeeee ee eee eeeeeeeeee eeeee eee eee eeee eeeeee eee eee eeeeeeee eeee ee eee eeeeee eeeee, eeeeeeeeee ee eee eeee eeee eeee eeee eeeeeeee ee eee e eeeeeeeeeeee eeee.

‌Meeeee 88‌ α-Meeeeeeeeee ee e Meeee Meee Meeee[‌888‌]

Meeeee eee eeeee eeeee eeee eeeeeeeeeeeeee(M) eeeeeeeeeee ee e 8:8 eeeeeee ee eeeeeeeeeeeeeee eee eeee-eeeee eeeeeee ee eee eeeeeeee ee eeeeeeeeeeeeeeeee eee M,M-eeeeeeeeeeeeeeeeeeeee ee eeeeeeeeeeeeeeeee eeeeee eee eeeeeeeeeeeee α-eeeeeeee eeeeeeee.[‌888‌] Mee eeeeeee, eeeeeeeee ee eeeeeeee-8-ee-8-eee (‌888‌) eeee eeeeeee eeeeeeeeeeeeee(M) eeeeeeeeeee eeeee eeeee eeeeeeeeee eeeeeeee eee eeeeeeee eeeeeeee ‌888‌ ee ee ee 88% eeeee (‌Meeeee 88‌). Meee eeeeeeee eee eeee ee eeee ee eee eeeeee eeeeeeeeeeeeeeee eeeee eeeeeeeee ee (–)-eeeeeeeeee.[‌888‌]

‌Meeeee 88‌ α-Meeeeeeee ee Meeeeeee-8-ee-8-eee Meeee Meeeeeeeeeeeee(M) Meeeeeeeeee[‌888‌]

‌Meeeeeeeeee 88‌

M-eeeeeeeee ee eeeeeeeeeeeeeee (‌888‌) ee eeeeeeee eeeee eeeeeeeeeeeeeeeeeeeeeeee(M) ee eee eeeeeeee ee eeeeee(M) eeeeeeee ee eeeeee eeeeeeeeeeeeeeeee (‌888‌) ee 88% eeeee (‌Meeeee 88‌).[‌888‌]

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

Meeeeeeeeeee Meeeeeeee

8-Meeeee-8,8-eeeeeeeeeeeeeeeee-8(8M)-eee (‌888‌):[‌888‌]

8-(Meeeeeeeeeeeeee)-8,8-eeeeeeeeeeeeeeeeee (‌888‌; 88 ee, 8.88 eeee) eee eeeee ee e eeeeeeeeee ee Me8MeM (888 ee, 8.88 eeee) ee MMM (8 eM) ee −88 °M eeeee eeeee, eee eee eeeeeee eeee eee eeeeeee eeeeeeeeeee. Mee eeeeeee eee eeeeeee ee ee eee 88 eee. Mee. ee MM8Me eee eeeee eee eee eeeeeee eee eeeeeeeee eeee MeMMe. Mee eeeeeee eeeeeeee eeee eeeee (Me8MM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeeee 8:88); eeeee: 88.8 ee (88%).

8-Meeeeeeeeeeeee-8-ee-8-eee (‌888‌, Me8 = Me); Meeeeee Meeeeeeee:[‌888‌]

M eeeeeee ee MM8Me8 eee e-MeMM (8:8; 8.88 eM) eee eeeee ee e eeeeeee ee Me8MeMe8 (888 ee, 8.88 eeee) eee eeeeeeee-8-ee-8-eee (‌888‌; 88 μM, 88 ee, 8.88 eeee), eeeeeeee ee eMe8MMe (88 μM, 88 ee, 8.88 eeee), eee Me8M (88 μM, 88 ee, 8.88 eeee). Mee eeeeeee eee eeeeeee ee ee eeeee eeeeeeee eeeeeeeeeee ee Me8MeMe8 eee eeeeeeee ee MMM (8–88 e), ee eeeee eeeee eee eeeeeee eee eeeeeeeeeeee eeee eeeeee eee. Meeeeeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeeee 8:8) eee eeeeeeeee ee eeee eee eeeeeee ee e eeeee eeeee; eeeee: 88 ee (88%).

References