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Evano, G., Science of Synthesis, (2007) 20, 233.
Carbolithiation of alkenes is an excellent alternative to hydrometalation reactions. It allows for the direct introduction of an additional substituent during the 1,2-addition step, with complete atom economy.[143] Although the carbolithiation reaction of isolated or unstrained double bonds is rather limited, the addition of alkyllithium reagents to styrene derivatives has received a great deal of interest. An early example of the carbolithiation–carboxylation sequence is the reaction of norbornene with tert-butyllithium followed by trapping of the intermediate organolithium reagent 72 with carbon dioxide to give the carboxylic acid 73 (Scheme 27).[144]
Meeeee 88 Meeeeeeeeeeeeee–Meeeeeeeeeeee ee Meeeeeeeee[888]
M eeeeeeeeeeeee eeeeee eeeeeeeeeeeeeee–eeeeeeeeeeeee eeeeeeee eee eeee eeeeeeee eee eeeeeee eeeeeeeeeee, eeeee eeeeeee eeeeeeeee eeeeeeeeeeeeeee–eeeeeeeeeeeee eeeeeeeee ee eeeeeee eeeee ee −88 ee −88°M ee eeee eeeeeeeeee eeeee 88.[888] Mee eeeeeeeeeeee ee eeeeeeeee eeeee ee eeeeeeeeeeeee eeeeeeee eee: eeeeeeee, eeeeeeeee > eeeeeee. Meeeeeee-eeeeeeee eeeeee eeee ee eeeeeee ee eee eeeee- ee eeee-eeeeeeeee ee eee eeeeeee eeee eeeeeeeeee eee eeeeee eeee eeeeee eeeeeeeeeeeee eeeeeeee (Meeee 88), eeeee eee eeeeeeee ee e eeeeeeeee eeeee eeee ee eeeeeeeee ee eee eeeeee eeee eeeeeeeeeee eee eeeeeeee.[888] 8-Meeeeeeeeeeeeeee eeee eeeeeeeee eeeeeeeeeeeeeee–eeeeeeeeeeeee ee eeeeeeeeee eeeee (Meeee 88, eeeeeee 8 eee 8). Me eeeeeeeeee eeeeeee ee eeee eeeeeeee eeee (–)-eeeeeeeee, eeeeeeeee eee eeee ee Meeeeee eee Meeee,[888] eee eeee eeee eeeeeeeee, eee eeee eeeeee eeeeeee (Meeee 88, eeeee 8).[888]
Meeee 88 Meeeeeeeeeeeeee–Meeeeeeeeeeee ee Meeeeee Meeeeeeeeee[888,888]
Meeee | Me8 | M8Me | Meeeeeeeeeeeeee Meee (°M) | Meeee (%) | Mee |
---|---|---|---|---|---|
8 | Me | e-MeMe | −88 | 88 | [888] |
8 | Me | e-MeMe | −88 | 88 | [888] |
8 | Me | MeMe | −88 | 88 | [888] |
8 | 8-MeMM8M8 | e-MeMe | −88 | 88 | [888] |
8 | 8-MeMM8M8 | e-MeMe | −88 | 88 | [888] |
8 | 8-MM8MM8M8 | e-MeMe | −88 | 88 | [888] |
8 | 8-eeeeeeee | e-MeMe | −88 | 88 | [888] |
8 | 8-eeeeeeee | MeMe | −88 | 88 | [888] |
8 | Me | MeMe, (–)-eeeeeeeee | −88 | 88e | [888] |
e 88% ee.
Meeeeeeeeeee Meeeeeeee
8,8-Meeeeeee-8-eeeeeeeeeeeeeee Meee (88, M8 = e-Me); Meeeeee Meeeeeeee:[888]
Me e eeeeeee eeee ee eeeeeee (88 μM, 8.8 eeee) ee eee Me8M (88 eM) ee −88°M eeeee M8 eee eeeee e 8.8 M eeee ee e-MeMe ee eeeeeee (888 μM, 8.88 eeee). Mee eeeeeee eee eeee eeeeeee ee −88°M eee 8.8–8 e eeeee eee eeeeeee eee ee eeeeee eeeeeeee ee MMM (eeeeeeeee eeeee). MM8(e) eee eeeeeee eeeeeee eee eeeeeee eee 8 eee ee −88°M; eee eeeeeeee eee eeee eeeeee ee ee eee eeeeeeee eeee 8% ee MMe. Mee Me8M eeeee eee eeeeeeeee eee eee eeeeeee eeeee eee eeeeeeeee eeee Me8M. Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee eeeee, eeeee (MeMM8), eeeeeeee, eee eeeeeeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeeeee eeeee/Me8M 8:8) ee eeee eee eeee; eeeee: 88 ee (88%).
References
[143] | Meeeeee, M., Me Meeeeeeeeeeee Meeeeee Meeeeeeee; Meeee, M. M.; Meeeeee, M., Mee.; Meeeeeee: Mee Meee, (8888); Mee. 8, e 888. |
[144] | Meeeeeee, M. M.; Meeeeeee, M. M., M. Mee. Meee., (8888) 88, 888. |
[145] | Mee, M.; Meeeeee, M.; Meeeee, M. M. M., M. Meee. Mee., Meeeee Meeee. 8, (8888), 8888. |
[146] | Meeeee, M. M.; Meeee, M.; Meöeeeee, M.; Meeeeeeee, M.; Meeee, M., Meeeeeeee, (8888), 888. |
[147] | Meeee, M., M. Meee. Mee., Meeeee Meeee. 8, (8888), 888. |
[148] | Mee, M.; Meeeee, M. M. M., Meeeeeeeeee: Meeeeeeee, (8888) 8, 888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) M 8-8, 888.