Science of Synthesis

Evano, G., Science of Synthesis, (2007) 20, 231.

Transition-metal catalysts provide powerful tools for 1,2-addition reactions to unactivated C=C bonds, such as hydrometalation. This enables the synthesis of carboxylic acids from alkenes by trapping the newly formed organometallic reagent with carbon dioxide. Finkbeiner and Cooper reported in the early 1960s that a mixture of propylmagnesium bromide and titanium(IV) chloride was an efficient catalyst for the hydromagnesiation of alkenes, placing the magnesium at the terminal position of the alkene, except when a benzylic Grignard can be formed. By reacting the obtained Grignard reagent with carbon dioxide, the carboxylic acids ‌64‌–‌67‌ were obtained (‌Scheme 24‌).[‌136‌,‌137‌]

‌Meeeee 88‌ Meeeeeeeee Meeee eeee Meeeeee ee Meeeeeeeeeeeeeeee–Meeeeeeeeeeee[‌888‌,‌888‌]

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‌Meeeee 88‌ Meeeeeeeee Meeee eeee Meeeee ee Meeeeeeeeeeeeee–Meeeeeeeeeeee[‌888‌,‌888‌]

Meeeeeeeee eeeeeeee ee eee eeeee eeeee eeeee eeeeeeeee eeeeee η8-eeeeeeeeeeeeeeee, Me(η8-eeeee) (Me*)8 (Me* = ee eeeeeeeee eeeeee eeeeeeeeeeeeeeee eeeee), eee eeee eeeeeeee. Meee, eee eeeeeeee eeee eeeeee eeeeeee eeeeeeee eeeeeeeee eeeeee 8-eeeeeeeee-8-eeeee eeee eee eee eeeeeeeeeee; eee eeeeeeeeeeee eeeeeeee eeeeeee ee eeee ee 88% ee eeeee e eeeeee η8-eeeee-(eeee-eeeeeeeeee)eeeeeeee eeeeeee ‌88‌ (‌Meeeee 88‌).[‌888‌]

‌Meeeee 88‌ Meeeeeeeee Meeee eeee Meeeee ee Meeeeeeeee Meeeeeeeeeeeeee–Meeeeeeeeeeee[‌888‌]

Meeeeee, eee eeee Meeeeeee eeeeeee eeeeeeeee(η8-eeeeeeeeeeeeeeee)eeeeeeeeeeeeeeee(MM) eee eeee eeeee ee eeeee eeee eeeeee eeeeeeee ee eeee ee eeeeeeeeeeee eeeeeeeeeeeee eeeeeee, eeeee eee eeee ee eeeeeeee ee eee eeeeeeeeeeeee eeeeeeeeee eeee. Meeeeee, eeee eeeeeeeeeeeeeeee eeeeeeee eee eeee eeee eeeeeee ee eee eeeeeeee ee eeee.[‌888‌]

Meeeeeeeeeee Meeeeeeee

8-Meeeeeeeeeeeee Meee (‌88‌); Meeeeee Meeeeeeee:[‌888‌]

MeMeMe eee eeeeeeee ee eeeeee MeMe (88 eM, 8.8 eee) ee Me8M (88 eM) ee Me (88.8 e, 8.88 eee) ee Me8M (888 eM) eeee e eeeeee ee 88 eee. Mee eeee eee eeee eeeeeeee eee 88 eee, eeeeee ee 8°M, eee eeeeeeeeeeee (88 e, 8.8 eee) eee MeMe8 (8 eM, 8 eeee) eeee eeee eeeee. Mee eeeeeee eee eeeeeeee eee 8 e, eeeeee ee 8°M, eee e eeeeeee eeeeeee ee MeMe8 (8.88 eM, 8 eeee) eee eeeee. Meeeeee eee eeee eeeeeeeee eee ee eeeeeeeeee 88 e eee eee eeeeeeeee eeee eeeeeee, eeeee eeeeeee eeeeeeee ee eeeeeee ee eee eeeeee eeeeee, eee eeeeee eeeeee eeeeee Me8M (888 eM). Mee eeeeeee eee eeeeee ee ee eee/eeee eeee, eeeeeee ee eeeee eeee eee MM8 ee −88 ee −8°M, eee eeee eeeeeeee eeee eee eee 88% M8MM8. Mee Me8M eeeee eee eeeeeeeee eee eeeeeeeee eeee 88% MeMM (8 × 88 eM), eeee eeee M8M eeeee eeee eeeeeeeee ee eeeeeeee eee eeeee eeee eeeeeeee ee eee eeeee eeeeeeeeee. Mee eeeeeeee eeeee eeeeeeee eeee eeeeeeeee ee eeeeeeeeeee eeeeeeee eeeee eeee ee eee eeeeeeee eeeeeee eeeeeeee eee eeeeeee, eee eeee eeeeee eee eeeeeeeee eeee eeeee MMe, eeeee eeeeee eee eeeeeeeeee ee e eeeeee eeeee eeee eee eeeeeeeee eeee Me8M. Meeeeee, eee eeeeeee eeeee eee eeeee (MeMM8), eeeeeeee, eee eeeeeeeeeeee ee eeeeee eee eeee eeee; eeeee: 88 e (88%).

References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) M 8-8, 888.