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1.1.5.7 α-Arylation of Carbonyl Compounds

DOI: 10.1055/sos-SD-204-00082

Mukherjee, S.Science of Synthesis: Asymmetric Organocatalysis, (20121265.

α-Arylation of carbonyl compounds is an extremely important transformation owing to the value of α-arylated carbonyl compounds in the pharmaceutical and chemical industries as well as in academia. Not too long ago, this transformation was considered to be the domain only of transition-metal catalysis. Even then, the scope of most asymmetric arylation methods was restricted to α-branched ketones and lactones, which generate a quaternary stereocenter adjacent to the carbonyl functionality. Catalytic enantioselective production of α-aryl carbonyl compounds containing an enolizable α-carbonyl benzylic stereocenter has only recently been realized through enantioselective Negishi and Kumada coupling of α-methine bromo ketones and amides with organometallic arenes at low temperature.

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Meeeeeeeeee 88

M8 ee (%) Meeee (%) Mee
Me 88 88 [‌88‌]
(MM8)8Me 88 88 [‌88‌]
eMe 88 88 [‌88‌]
(MM8)8MM8Me 88 88 [‌88‌]
(MM8)8MMe 88 88 [‌88‌]
(MM8)8MMMee 88 88 [‌88‌]
(M)-(MM8)8MM=MMMe 88 88 [‌88‌]
88 88 [‌88‌]
8:8e 88 [‌88‌]
>88:8e 88 [‌88‌]

e ee.

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Meeeee 88 Meeeeeeee Meeeeeeeee α-Meeeeeeee ee Meeeeee[‌88‌]

Meeeeeeeeee 88

Me8 ee (%) Meeee (%) Mee
8-M8MM8M8 88 88 [‌88‌]
8-MeM8MM8M8 88 88 [‌88‌]
8-MeM8M8 88 88 [‌88‌]
8-MeM8M8 88 88 [‌88‌]
8-Mee 88 88 [‌88‌]
8-M8MM8M8 88 88 [‌88‌]
8-eeeeeeee 88 88 [‌88‌]
8-MeM8M8 88 88 [‌88‌]
8-MeMM8M8 88 88 [‌88‌]
8,8-M8M8M8 88 88 [‌88‌]
8-eeeeeee 88 88 [‌88‌]
88 88 [‌88‌]

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Meeeee 88 Meeeeeeeeee ee α-Meeeeeeee ee eee Meeeeeeeeeeeeeee Meeeeeeee ee (M)-Meeeeeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

(M)-8-Meeee-8-eeeeeeeeeeeeee 888; Meeeeee Meeeeeeee:[‌88‌]

Me ee eeee-eeeee 8-eM eeee eeeeeeee eeee e eeeeeeee eeeeeee eee eee Meeeee eeeeee eeee eeeee eee eeeeeeeeeeeeeee eeee eeee ee (8M,8M)-8-eeee-eeeee-8-eeeeee-8-eeeeeeeeeeeeeeeeee-8-eee (888; 88.8ee, 8.88 eeeee), MeMe (88.8ee, 8.88 eeeee), MeMMM8 (888.8ee, 8.88 eeeee), eee eeeeeeeeeeeeeeee eeeeeeeeeeeeeeeeeeeeeeee (888; 8.88 eeeee). Mee eeee eee eeeeee eee eeeeee eeee e eeeeee ee eeeee. Meeeeee (8.8eM) eee Me8M (8.8eM) eeee eeeee, eeeeeeee ee eee eeeeeeee 888 (8.88eeee, 8.88 eeeee). Meeee 888e, eee eeeeeee eee eeeeeee eeee MM8Me8 (8.8eM) eee eeeeee ee 88°M. MeMM8 (888.8ee, 88.8 eeeee) eee eeee eeeee, eeeeeeee ee eeee MeMM (8.8eM; 88°M). Mee eeeeeee eee eeeeeee eee 8e ee 88°M, eee eeee eeeeeeeeeee ee e eeeee eeeeeeeeee eee. ee MM8Me (88eM). Mee eeeeeee eeeee eee eeeeeeeee eeee MM8Me8 (8×88eM), eee eee eeeeeeee eeeeeee eeeeee eeee eeeee (MeMM8) eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeee eee eee eeee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee); eeeee: 8888%; 8888% ee.

(M)-8-Meeeeeeee-8-eee 888; Meeeeee Meeeeeeee:[‌88‌]

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(M)-8-(8-Meeeeeeeeeeee)eeeeeeeee Meee (888); Meeeeee Meeeeeeee:[‌88‌]

Me ee eeee-eeeee 8-eM eeee eeeeeeee eeee e eeeeeeee eeeeeee eee eee Meeeee eeeeee eeee eeeee eee eeeeeeeeeeeeeee eeee eeee ee (8M,8M)-8-eeee-eeeee-8-eeeeee-8-eeeeeeeeeeeeeeeeee-8-eee (888; 88.8ee, 8.888eeee, 8.88 eeeee), MeMe (8.8ee, 8.888eeee, 8.88 eeeee), MeMMM8 (88.8ee, 8.88eeee, 8.8 eeeee), eee (8-eeeeeeeeeeeee)(eeeeeee)eeeeeeee eeeeeeeeeeeeeeeeeeeeeeeee (888; 888ee, 8.88eeee, 8.88 eeeee). Mee eeee eee eeeeee, eeeeee eeee e eeeeee ee eeeee, eee eeeeee ee 8°M. Meeeeee (8.88eM) eee Me8M (8.88eM) eeee eeee eeeee, eeeeeeee ee eeeeeeee (88µM, 8.88eeee, 8.88 eeeee). Meeee 8e, eee eeeeeee eee eeeeeeeeeee ee e 88-eM eeeee-eeeeeeee eeeee eee eeeeeee eeee MeMM (8.88eM). Me eee eeeeeee eee eeeee (eeeeeeeeeeeee)eeeeeee (888ee, 8.88eeee, 8.88 eeeee), MMMMM (88.8ee, 8.88eeee, 8.88 eeeee), eee M8M (8.88eM). Mee eeeeeee eee eeeeeee ee ee eee 8e, eeee eeeeeeee eeee eee. Me8M8M8 (88eM), eee eeeeeee eeee MeMMe (88eM). Mee eeeeeee eee eeeeee eeee e eeeeeeeeee eeeeee eee eee eeeeeee eeeee eee eeeeeeeee eeee 8M MeMM (8×). Mee eeeeeee eeeeeeee eeee eeee eeeeeeeee eeee 8M MMe (eeeee eM <8) eee eeeeeeeee eeee MM8Me8 (8×). Mee eeeeeee eeeeee eeee eeeeeeee, eeeee (MeMM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (8888% MeMMe/eeeeeee eeee 8% MeMM) ee eeeeeee eee eeeeeee ee e eeeee eeeee; eeeee: 88.8ee [88% (eee eeeee)]; 88% ee.

References


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