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Please login to access the full content or check if you have access via43.8.2.3.3 Method 3: Base-Catalyzed Rearrangement of Internal Alkynes
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Krueger, A., Science of Synthesis, (2008) 43, 506.
In the case of functionalized or branched internal alkynes, the rearrangement to isomeric internal alkynes can be used preparatively as well. Branching hinders the migration of the triple bond to the terminal carbon atom owing to the lack of the necessary proton at the branching points (see also Section 43.8.2.3.2).[150] Some functional groups, such as carboxy and ester groups, also favor the formation of internal isomers. Usually, the triple bond migrates away from electron-withdrawing groups.[145]
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Meeeee 88 Meee-Meeeeeeee Meeeeeeeeeeee ee Meeeeeee Meeeeeeeeeeeee[888]
M8 | Meeeeeeeee | Meeee (%) | Mee |
---|---|---|---|
e-Me | 88°M, 88 e | 88e | [888] |
MMMeMe | 88°M, 88 e | 88e | [888] |
e Meeeeeee eeee 88% ee eee eeeeeeee eeeeeeee.
e Meeeeeee eeee 88% ee eee eeeeeeee eeeeeeee.
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Meeeee 88 Meee-Meeeeeeee Meeeeeeeeeeee ee Mee-8-eeeee Meeee ee Mee-8-eeeee Meeee[888,888,888]
M8 | Meeeeeeeee | Meeee (%) | Mee |
---|---|---|---|
Me | 88% ee MMM, 88°M, 8 e | 88 | [888] |
Me | MeMM8, eee MM8, −88 ee −88°M, 8 e | 88 | [888,888] |
Me | MeMM8, eee MM8, −88 ee −88°M, 8 e | 88 | [888] |
Me | MeMM8, eee MM8, −88 ee −88°M, 8 e | 88e | [888] |
e Me e eeeeeee eeee eeeee-8,8-eeeeeee eeee (88%).
Me ee eeee eeeeeeee ee eeeeeeeee α-eeeeeeeeee eeeeeee 888 eeee eeeee β-eeeeeeeeeee 888; eee eeeeee eee eeeeeee 88 eee 88% (Meeeee 88).[888] Meeeeee, eeeeeeeee eeee-eeeeeeee ee eeeeeeee eeeeeeeee ee eeee ee eee eeeeeeee. Me eeee eeeee, eee eeee ee eee eeeeeee eeeeeeee eeeee ee eeeeeeeeeeee.
Meeeee 88 Meee-Meeeeeeee Meeeeeeeeeeee ee α-Meeeeeeeee Meeeeee[888]
Me e eeeeeee eeeeeee, α-eeeeeeeeee eeeee eeeeee eee ee eeeeeeeeee eeee eeeeeeeee eeee-eeeeeeee ee eeeeeeee eeeeeeeee ee eee eeeeeeee ee e eeeee eeeeee ee eeeeeeeeeeeeeeeeeeee eeeeeeee.[888] Meeeeee, eeee eeeeeeeeeeeee ee eeeee eeeeeeee eee eeeeeee eeeeeeeeeee eeeeeeee eee eeeeeeee.
Meeeeeeeeeee Meeeeeeee
Meee-8-eeeee eeee (888, M8 = Me); Meeeeee Meeeeeeee:[888]
MMMMMMM: Meeeee eeeee eeeeeeeeee eeeeeee ee eeeeeeee ee eeeeeee ee eeeeeeee ee eee eee eee eeee ee e eeeeee eeeeeeee.
M eeeeeee eeeeeeeeee ee MeMM8 (88 e, 8.8 eee) ee eee MM8 (888 eM) eee eeeeeeee. Meee-8-eeeee eeee (888, M8 = Me; 8.8 e, 8.8 eee) ee MMM (88 eM) eee eeeee eeee e eeeeeee, eeeeeee eee eeeeee e eee ee eeeee eee eeeeeee ee eee MM8. Mee eeeeeee eeeeeee eeeeee eeee e eeeee, eeeee eeeeeeeeee. Meeee eeeeeeee eee 88 eee, MM8Me (88 e) eee eeeee eeee 8 eee eeeee eeeee eeeeeeee. Meeee eeeeeeeeeee ee eee MM8 (ee e 88°M eeeee eeee, eeee eeeeeeee ee eee eeeee), Me8M (888 eM) eee eeeee eee eee eeeeeee ee 88°M eee eeeeeeeee eeeee eeeeeeeeeee ee eee eeee eeeeee ee MM8 eee eeeeeee eeeeeeeeee. Mee eeeeeee eee eeeeee ee ee eee eeeeeee eee (888 e) eee eeee eeeee, eeeee eeeeeeeee eee eeeee eeeeeeee. Meeeeeeeee eeeeeeee ee 8 M MMe eee eeeeeeeee eeeee eee eM eeeeeee eeee eeee 8. Mee eeee eee eeeeeeeee eeee MM8Me eee eeeeeeeee eeee Me8M (88 ×). Mee eeeeeee eeeee eee eeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeee eeeee eee eeeeeeeeeeeeee (eeeeeee) ee eeee eee eeeeeee ee eeeeeeeee eeeeeee; eeeee: 8.8 e (88%); ee 888–888°M.
References
[145] | Meeee, M. M., Me Meeeeeeee ee Meeeeeeeee, Meeee, M. M., Me.; Meeeee: Mee Meee, (8888); e 888. |
[148] | Meeeeeee, M., Meeeeeeeeee Meeeeeeeee Meeeeeeee, 8ee ee., Meeeeeee: Meeeeeeee, (8888); e 888. |
[150] | Meeee, M. M.; Meeeeee, M. M.; Meeeeeeee, M. M., M. Mee. Meee., (8888) 88, 8888. |
[156] | Meeee, M. M. M.; Meeeeee, M. M.; Meeeeee, M. M., M. Meee. Mee., (8888), 8888. |
[169] | Meeeeeee, M., M. M. Meeeeee Meee. Mee., Mee. M, (8888) 888, 88. |
[170] | Meeeeeee, M.; Meeeee, M. M.; Meeeee, M. M.; Meeeeee, M., Meee. Mee. Meee. Me., (8888), 8888. |
[172] | Meeee, M. M.; Meeee, M., M. Meee. Mee., (8888), 8888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) 8/8e, 888.
- 8.Meeeee-Meee, (8888) 8/8e, 888.
- 8.Meeeee-Meee, (8888) 8/8e, 888.