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45.4.2.1.1.8 Variation 8: Friedel–Crafts Alkylation of Arenes with Aldehydes

DOI: 10.1055/sos-SD-045-00097

Zysman-Colman, E.Science of Synthesis, (201045168.

Diarylation of alkyl and aryl aldehydes using a dual catalyst system comprising iridium(I) and tin(IV) cleanly affords diarylmethanes and triarylmethanes (e.g., 9), respectively, in moderate to good yields under solvent-free conditions (Scheme 13).[‌46‌] Aluminum trichloride, under solvent-free conditions, also catalyzes the reaction to give alkylarenes 9.[‌47‌] Aromatic aldehydes bearing electron-withdrawing groups are the best substrates, while yields are much poorer with formaldehyde, alkyl aldehydes, and aryl aldehydes with electron-donating substituents. Most other Lewis acid catalyzed alkylations of arenes with aldehyde electrophiles do not cleanly produce diarylmethanes or triarylmethanes.[‌48‌]

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Meeeee 88 Meeeeeeee ee Meeeeeeeeeeeee eee Meeeeeeeeeeeeee Meeee Meeeeee(M)/Mee(MM), Meee(MMM) Meeeeeee, ee Meeeeeee Meeeeeeeeee Meeeeeeee[‌88‌,‌88‌,‌88‌]

Meeeeeeeeee 88

M8 Me8 Meeeeee Meee (e) Meeee (%) Mee
8-M8MM8M8 8-MeMM8M8 M 8.8 88 [‌88‌]
8-M8MM8M8 8,8-(MeM)8M8M8 M 8.8 88 [‌88‌]
8-M8MM8M8 8,8,8-(MeM)8M8M8 M 8 88 [‌88‌]
8-M8MM8M8 8,8,8-(MeM)8M8M8 M 88 88 [‌88‌]
Me 8,8,8-(MeM)8M8M8 M 88 88 [‌88‌]
8-M8MM8M8 8,8-(MeM)8M8M8 M 88 88 [‌88‌]
8-M8MM8M8 8-MMM8M8 M 8 88 [‌88‌]
Me 8-MeMM8M8 M 8 88 [‌88‌]
8-M8MM8M8 8-MeMM8M8 M 8 88 [‌88‌]
8-MeMM8M8 8-MeMM8M8 M 8 88 [‌88‌]
8-M8MM8M8 8-MM-8-MeM8M8 M 8 88 [‌88‌]
8-M8MM8M8 8-MM-8-MeM8M8 M 88 88 [‌88‌]
8-M8MM8M8 8-MMM8M8 M 8 88 [‌88‌]
8-MeM8M8 8-MeMM8M8 M 8.8 88 [‌88‌]
8-MMMM8M8 8-MeMM8M8 M 8 88e [‌88‌]
8-MeM8M8 8-MeMM8M8 M 8 88 [‌88‌]
8-MeM8MM8M8 8-MeMM8M8 M 8 88 [‌88‌]
8-MM8MM8M8 8-MeMM8M8 M 8 88 [‌88‌]
Me 8-MeMM8M8 M 8 88 [‌88‌]
8-Mee 8-MeMM8M8 M 88 88 [‌88‌]
M 8-MeMM8M8 M 8 88 [‌88‌]
Me 8-MeMM8M8 M 88 88 [‌88‌]

e Meeeee M: eeeeeeee (8eeee), eeeee (8eeee), [MeMe(eee)]8 (8.88eeee), MeMe8 (8.88eeee), 88°M; Meeeee M: eeeeeeee (8eeee), eeeee (8eeee), MeMe8/8MeMMe (8.88eeee), 88°M; Meeeee M: eeeeeeee (8eeee), eeeee (8eeee), MeMe8/8MeMMe (8.88eeee), 88°M; Meeeee M: eeeeeeee (8eeee), eeeee (8eeee), MeMe8 (8.8eeee), ee.

e Meeeeeee eeeeee ee eeee eeeeeeee eeeeee ee eeeeeeeeeeeeeeeeee ee eeee eee 8,8-eee(eeeeeeeeeeee)eeeeeee.

Meeeee 88 Meeeeeeee ee Meeeeeeeeeeeee Meeee Meeee MeeeeeeeeeeMeeeeee Meeee Meeeeee ee Meeeeeee[‌88‌]

Meeeeeeeeee 88

Me8 Me8 Meeeeeeeee Meeee (%) ee 88 Mee
Me Meee eeeeee, 88e 88 [‌88‌]
Me 8,8-Me8M8M8 eeeeeeeee, 888°M, 8e 88 [‌88‌]
Me Me eeeeee, 88e 88 [‌88‌]
8-Mee Me eeeeeeeee, 888°M, 8e 88 [‌88‌]

e Meeeeee eeeeeeeeeeee 8-Mee/8-Mee/8-Mee ee. 88:8:88.

Meee eeeeeeee(MMM) eeeeeeeeeeeeeeeeeeeeeeeee ee eeee ee eee eeeeeeee ee eee eeeeeeee ee eeeeeee-8,8-eeee, eeeee eeeeeeeee eee eeeeee ee eeee, eeeeeeeeeee eee eeeeeeeeeeeee eeeeeeeeeeeeee 88 eee ee eeeeeeee ee eeeeeeeee eeee ee eeeeeeeee eeeeee (Meeeee 88).[‌88‌,‌88‌] Meeeeeeeeeeee ee eeee eeeeeeeee ee eee eeeeeeeeeeeeeeeee, eeeeeeee eeeeeeee eee eeeeeee eeee ee eeeee eeee eeee eeeeeeeeeeee eee eee eeeee ee eee eeeee ee eeeeeee ee eeeeeeee eeeeeeeee eeeeee; eee eee ee eeeeee eeeeeeeee eeeeee eeee ee eeeeeee eeeeeee ee eeeee eeeeee ee eeeee eeee eee eeeeeeee eeeeeeee. Mee eeeeeeee eeeeeeee eee e eeeee eeeeeeeee eee ee eeeeeeeee eee eeeeeeeeeeeeee; eeeee eeeeee eeeeeeee eeee ee eeeeeeeeeeeeeee eee eeeeeeeeeee eee eee eeeeeeee ee eee eeeeeeee eeeeeee.

Meeeee 88 Meeeeeeee ee Meeeeeeeeeeeee eeee Meeeeeeeeeeeeeeeee eee Meeeee[‌88‌,‌88‌]

Meeeeeeeeeee Meeeeeeee

Mee(8-eeeeeeeeeeeee)(8-eeeeeeeeeee)eeeeeee (8, Me8=8-MeMM8M8; M8=8-M8MM8M8); Meeeeee Meeeeeeee Meeee ee Meeeeee(M)/Mee(MM) Meeeeeee:[‌88‌]

M 88-eM Meeeeee eeeee eeeeeeee eeee e eeeeeeee eeeeeee eee eee eeeeeee eeee [MeMe(eee)]8 (8.88eeee), MeMe8 (8.88eeee), eee eeeeeee (888ee, 8eeee). Mee eeeee eee eeeeeeee eeee eeeee eee eeeeee ee e eeeeeeee-eeeeeeeeeee eeee ee 88°M. Mee eeeeeee eee eeeeeee eeeeeeeeee eee 8eee, 8-eeeeeeeeeeeeeeeee (888ee, 8eeee) eee eeeee eee eee eeeeeeee eee eeeeeee ee eeeeeeee ee 88°M [MMM eeeeeeeeee; eeeeeeeee eeeee (ee 8888°M)/MeMMe 8:8]. Meeee eeeeeeeeee ee eee eeeeeeee, eee eeeeeee eee eeeeeeee eeee ee MM8M eee eeeeeeeee eeee Me8M. Mee eeeeeeee eeeeeeee eeee eeeeee eeee M8M eee eeeee, eeee eeeee (MeMM8), eee eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee. Meeeeeeeeeee ee eeeeee eeeeeeeeeeeeee [eeeeee eee, eeeeeeeee eeeee (ee 8888°M)/MeMMe 88:8] eeeeeeee eee eeeeeeeeeeeeee ee eee eee(8-eeeeeeeeeeeee) eeeeee; eeeee: 888ee (88%); Me 8.88 [eeeeeeeee eeeee (ee 8888°M)/MeMMe 8:8]; eeeee eeee eee eeeeeeeeeee (8-eeeeeeeeeee)(8-eeeeeeeeeeeee)(8-eeeeeeeeeeeee)eeeeeee; eeeee: 88ee (88%); Me 8.88 [eeeeeeeee eeeee (ee 8888°M)/MeMMe 8:8].

Meeeeeeeeee 8; Meeeeee Meeeeeeee Meeee Meeeeeee Meeeeeeeeee:[‌88‌]

MMMMMMM: Meeeeeee eeeeeeeeeee eeee ee e eeeeee eeeeeeee ee eee eeeeeee eee eeeeee eeeeeeeee eeee eeeee.

Me e eeeeeee ee eeeee MeMe8 (8.8eeee eee eeeeeeee eeeeeeeee; 8.8eeee eee eeeeeeeee eeeeeeeee) eee eee eeeee (8eeee eee eeeeeeeee eeeeeeeee; 8eeee eee eeeeeeee eeeeeeeee) eee eeeee eee eeeeeeee (8eeee) eeeeeeee ee ee. Mee eeeeeeeee eeeeeee eee eeeeeee eee 8e (eee eeeeeeee eeeeeeeee) ee 88e (eee eeeeeeeee eeeeeeeee). Mee eeeeeeee eee eeeeeeeee eeeeeeeeee eeee M8M (88eM) eee eee eeee eee eeeeeeeee eeee Me8M (8×88eM), eeeee (Me8MM8), eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeeeee eeeee/MeMMe 88:8) ee eeeeee eee eeeeeee eeeeeee; eeeee: 8888%.

(8-Meeeeeeeeeee)(8-eeeee)eeeeeee (88, M8=Me; M8=8-Me), (8-Meeeeeeeeeee)(8-eeeee)eeeeeee (88, M8=Me; M8=8-Me), eee (8-Meeeeeeeeeee)(8-eeeee)eeeeeee (88, M8=Me; M8=8-Me); MeeeeeeMeeeeeeee:[‌88‌]

M 88-eM, eee-eeeeee, eeeee-eeeeeeee eeeee, eeeeee eeee e eeeeee eeeeeeeee, eee eeeeeee eeee Me(MMe)8 (8.888e, 8.8eeee). Mee eeeee eee eeeeee ee 888°M eeeee eeeeeee eeeeeeee eeeeeeeee. Mee eeeee eee eeeeee ee ee eee eeee eee eeeeeeeeeeee eeeeeee eeee eeeeeee (8.8eM), eeeeeee-8,8-eeee (88ee, 8.8eeee), eee 8-eeeeeeeeeeeeeeeeee (888ee, 8.8eeee) ee ee, eeee eeeeeeee. Mee eeeee eeeeeee eee eeee eeeeee ee eeeeee eeeeeeeeeee eee 88e eeeee eeeeeeee, eeeeee ee ee, eee eeeeee eeee M8M. Mee eeeeeee eeeee eee eeeeeeeee, eee eeeeeee eeeee eee eeeeeeeee eeee Me8M, eee eee eeeeeeee eeeeeee eeeeeeee eeee eeeee (MeMM8); eeeee: 888ee (88%). MM/MM eeeeeeee eeeeeeee eee eeeeeeee ee ee eeeeeeee eeeeeee ee eeeeeeee, eeee eeeeee eeeee eeeeeeeeee eeee eeeeeeeeeee ee eee eeeeeeee eeeeeeee. Mee eeeeee eeeee ee eee eeeee-, eeee-, eee eeee-eeeeeeeeeee eeeeeeeeeeeeee eee eeeeeeeee ee MM ee ee 88:8:88, eee eee eeeeeeeee eeeee eeee eeeeeeee eeee eeeee ee eee eeeeeeeee eeeeeee.

References


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