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3.4.2.2.2.1 Addition of Alkenyl and Aryl Groups to Carbonyl Compounds

DOI: 10.1055/sos-SD-206-00122

Mase, N.Science of Synthesis: Water in Organic Synthesis, (20121164.

Transition-metal-catalyzed alkene hydroarylation has become an important strategy for alkylarene synthesis; rhodium catalysts, in particular, can be employed in water and under an atmosphere of air.[‌24‌] The intriguing insensitivity of the rhodium catalytic system toward water and air enables simple operation in organic syntheses. A number of alkene hydroarylations catalyzed by various rhodium(I) complexes have been reported, for example conjugate addition reactions of organostannanes,[‌25‌‌28‌] organobismuths,[‌27‌,‌29‌] diaryldichlorosilanes,[‌30‌] and perfluoroarenes[‌31‌] to α,β-unsaturated carbonyl compounds. The use of either organoboranes[‌32‌‌34‌] or organosilicons[‌35‌] is favorable based on considerations of toxicity, safety, versatility, and commercial availability; Scheme 12 shows examples for both of these reagent types. It is notable that the conjugate addition reactions of organosilicon reagents with α,β-unsaturated ketones, esters, and amides, and but-2-enenitrile, does not need any additive such as a fluoride source or base; in addition, the end product from the organotrialkoxysilanes is only harmless silica.[‌35‌]

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Meeeeeeeeee 88

M8 M8 M8 M Meeeeeee (eee%) Meeeeee Meee (e) Meeee (%) Mee
Me Me 8-Mee M(MM)8 [MeMe(eee)]8 (8.8) M8M 8 88 [‌88‌]
Me Me 8-Mee M(MM)8 [MeMe(eee)]8 (8.8) M8M 8 88 [‌88‌]
(MM8)8 8-Mee M(MM)8 [MeMe(eee)]8 (8.8) M8M 8 88 [‌88‌]
MMe Me 8-Mee M(MM)8 [MeMe(eee)]8 (8.8) M8M 8 88 [‌88‌]
(MM8)8 Me Me(MMe)8 [Me(eee)(MMMe)8]MM8 (8) 8,8-eeeeeee/M8M (88:8) 88 88 [‌88‌]
Me Me Me Me(MMe)8 [Me(eee)(MMMe)8]MM8 (8) 8,8-eeeeeee/M8M (88:8) 88 88 [‌88‌]
Me Me Me Me(MMe)8 [Me(eee)(MMMe)8]MM8 (8) 8,8-eeeeeee/M8M (88:8) 88 88 [‌88‌]
Me Me Me Me(MMe)8 [Me(eee)(MMMe)8]MM8 (8) 8,8-eeeeeee/M8M (88:8) 88 88 [‌88‌]
Me M Me Me(MMe)8 [Me(eee)(MMMe)8]MM8 (8) 8,8-eeeeeee/M8M (88:8) 88 88 [‌88‌]
Me Me MM=MMMe Me(MMe)8 [Me(eee)(MMMe)8]MM8 (8) 8,8-eeeeeee/M8M (88:8) 88 88 [‌88‌]
(MM8)8 MM=MMMe Me(MMe)8 [Me(eee)(MMMe)8]MM8 (8) 8,8-eeeeeee/M8M (88:8) 88 88 [‌88‌]
MMe Me Me Me(MMe)8 [Me(eee)(MMMe)8]MM8 (8) 8,8-eeeeeee/M8M (88:8) 88 88 [‌88‌]
MM8 Me Me Me(MMe)8 [Me(eee)(MMMe)8]MM8 (8) 8,8-eeeeeee/M8M (88:8) 88 88 [‌88‌]

Meeeeeeeeeee Meeeeeeee

β-(8-Meeee) Meeeeeee Meeeeeeee 88 (M8=8-Mee); Meeeeee Meeeeeeee:[‌88‌]

M eeeee eee eeeeeee eeee [MeMe(eee)]8 (8.888eeee) eee 8-eeeeeeeeeeee eeee [88, M8=8-Mee; M=M(MM)8; 8.8eeee], eee eeeeeee eeee eeeee. M8M (8eM) eee ee α,β-eeeeeeeeeee eeeeeeee eeeeeeee (8.8eeee) eeee eeee eeeee. Mee eeeeeee eee eeeeeee eee 8e ee 88°M. Mee eeeeeee 88 (M8=8-Mee) eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee); eeeee: 8888%.

8-Meeeeeeeeeeeeeeeeeee [88, M8,M8=(MM8)8; M8=Me]; Meeeeee Meeeeeeee:[‌88‌]

Me e eeeeeee ee eeeeeeeee-8-eeeee (88.8ee; 8.8eeee) eee [Me(eee)(MMMe)8]MM8 (8.8ee, 8.88eeee) ee 8,8-eeeeeee (8eM) eee M8M (8.8eM) eee eeeee eeeeeeeeee(eeeeee)eeeeee [88, M8=Me; M=Me(MMe)8; 888ee; 8.8eeee] eee eee eeeeeee eee eeeeeee ee 88°M eee 88e. Meeeee (888888eM) eee eeeee ee eee eeeeeee eee eee eeeeeeeee eeeeeeeeeee eee eeeeeee ee eeeeeeeeee. Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee/MeMMe 88:8) ee eeeeeee 8-eeeeeeeeeeeeeeeeeeee [88, M8,M8=(MM8)8; M8=Me]; eeeee: 888ee (88%).

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