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Please login to access the full content or check if you have access via36.9.1.8 Method 8: Reactions of Aldehydes/Ketones with α-Halo Ketones (Reformatsky Reaction)
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Mahrwald, R.; Schetter, B., Science of Synthesis, (2008) 36, 944.
The original Reformatsky reaction involves the treatment of an aldehyde or ketone with zinc and an α-halide. The halide is usually an α-bromo ester, vinylogous ester, nitrile, ketone, or amide.[564] This transformation is very similar to the Grignard reaction,[565,566] and is a useful means of synthesizing β-hydroxylated carbonyl compounds. The original reaction has been optimized and this development has been reviewed several times;[567–574] in addition, there are a number of related methods that use metals other than zinc. High yields are obtained when the Reformatsky reaction and its variations are used with activated zinc,[575] chromium(II) salts,[576] indium,[577] manganese,[578] low-valent titanium compounds,[579] samarium(II) iodide,[580] a combination of cadmium(II) chloride and metallic samarium,[581] or a combination of bismuth(III) chloride and metallic samarium,[582] germanium salts,[583] cobalt catalysts,[584] rhodium catalysts,[585] tin compounds,[586] iron catalysts,[587] scandium(III) trifluoromethanesulfonate,[588] and palladium catalysts.[589] Solid phase reactions are also known,[590] and even reactions in water are reported.[591]
β-Meeeeeeeeeee eeeeeeee eeeeeeeee eee ee eeeeeeee eeee eeee eeeeeee ee eeeeeeeeeeeeeeeeee ee eeeee eeeeee eeeeeee[888–888] ee eeeeee eeeeeeeee,[888] eee ee eee eeee, eeeeee eeeeeeeeeee, eeeeeeeeee eeeeee eeeeeeeeeeee eee eeeeeeee.[888,888] Meeeeeee ee eeeeeee, eee-eeeeeeeeee eeeeeee eee eeeeee,[888] eeeeee ee eee Meeeeeeeeee eeeeeeee 888M eee 888M eee ee eeeeeeee eeee eee eeeeeeeee ee M-(8-eeeeeeeee)eeeeeeeeee-8-eeee 888 eeee eeeeeeeee eeeeee ee eeeeeee eee eeeeeeeeee (Meeeee 888).[888]
Meeeee 888 Mee Meeeeeeee ee Meeeeee Meeeee Meeeeeeeeee eee Meeeeeeee Meeeeeee Meeeeeeeee ee eee Meeeeee ee Meeeeeeeeee Meeeeeeee Meeee Meeeee Meeeeeeeeeee ee Meeeeeeeeee[888,888]
M8 | M8 | M8 | M8 | Meeeeeeeee | Meeee (eeee/eee) | Meeee (M/M)e,e | Meeee (%) | Mee |
---|---|---|---|---|---|---|---|---|
eMe | Me | eMe | M | MeMe8/MeM, MMM, 88°M | 88:88 | >88:8 | 88 | [888] |
eMe | Me | Me | M | MeMe8/MeM, MMM, 88°M | >88:8 | >88:8 | 88 | [888] |
Me | Me | eMe | M | MeMe8/MeM, MMM, 88°M | 88:88 | >88:8 | 88 | [888] |
Me | Me | Me | M | MeMe8/MeM, MMM, 88°M | 88:88 | 88:8 | 88 | [888] |
eMe | M | Me | M | MeMe8/MeM, MMM, 88°M | >88:8 | e.e. | 88 | [888] |
Me | M | Me | M | MeMe8/MeM, MMM, 88°M | 88:88 | e.e. | 88 | [888] |
Me | Me | M | M | Me, MMM, −88°M, 88 e | 88:88 | e.e. | 88 | [888] |
Me | Me | Me | Me | Me, MMM, −8°M, 8 e | 88:88 | e.e. | 88 | [888] |
Me | Me | Me | Me | Me, MMM, −88°M, 8 e | 8:88 | e.e. | 88 | [888] |
e e.e. = eee eeeeeeee.
e Meeeeeeeeeeee ee eee eeeeeeee α ee eee eeeeeeee eeeee.
Meee eeeeeeeeeeeeee eeeeeee eee ee eeeeeeeee eeee ee Meeeeeeee–Meeeeee eeeeeeeeee eeeee ee Meee-Meeeeee–Meeeeeee eeeeee (Meeeee 888).[888]
Meeeee 888 Meeeeeeee–Meeeeee eee Meee-Meeeeee–Meeeeeee Meeeeeeeee Meeeee[888]
Mee eeeeeee ee eeeeeeeeeeeeeeeeeeee ee Meeeeeeeeee eeeeeeeee ee eeee eeeeeeee ee eeeeee eeeeeeeee, eee eeee eeeee 8-eeeeeeeeeeeeeee (888) ee eeeeeee eeee eeeeeeeeeeeee ee eee eeeeeeee ee eeeeee eeeeee ee eeeeee(M) eeeeeee eee eeee-eeeeeeeeee Meeeeeeeeee eeeeeeee 888 eee eeeeeee (Meeeee 888).[888]
Meeeee 888 Meeeee-Meeeeeee Meeeeeeeeee Meeeeeeee[888]
M8 | Meeeeeee | Meee (e) | Meeee (eeee/eee) | Meeee (%) | Mee |
---|---|---|---|---|---|
Me | Me | 8.8 | 88:88 | 88 | [888] |
8-Mee | Me | 8.8 | 88:8 | 88 | [888] |
8-Mee | MeMe | 8.8 | 88:88 | 88 | [888] |
8-MeM8M8 | Me | 8.8 | 88:88 | 88 | [888] |
Meeeeeeeeee, eeeeeeeee eeee eee eeeeeeeeeeeeeeeeeeeeee ee “eeeeeee” Meeeeeeeeee eeeeeeee 888 eee eeeeeeee eeee eee eeeeee 888 ee eeeeeee eeee eeeee eeeeeeeeeee eeeee eeeeee(M)-eeeee (MeM) eee eeeeeeeeeeeeeeeee (Meeeee 888).[888]
Meeeee 888 Meeeee-Meeeeeee eee-Meeeeeeee Meeeeeeeeee Meeeeeeee eeee Meeeeeeeeeeeeeeee[888]
Meeeeeeee Meeeeeeeeee eeeeeeeee eeeeeee eeeeeeeeeeee eee α-eeee eeeeee ee eeeeee eee eeeee eeeee eeeeeeeeeeee(MM) ee eee eeeeeeee ee eeeeee eeeeeeeee–eeeee eeeeeeeee; eeee eeee eee eeeeeeeeeeeee β-eeeeeee eeeeee ee eeeeee 888, eeeeeeee eee eeeeee eeee eee eeeeee eeee eeeee (Meeeee 888).[888]
Meeeee 888 Meeeeeeeeeee(MM) ee eee Meeeeeee ee Meeeee Meeeeeeee-eeeee Meeeeeeee eee Meeeeeeee Meeeeeeeeeeeeeee Meeeeeeeeee Meeeeeeee[888]
M8 | Meeeeeeeee (%) (MMMM) | ee (%) | Meeeee (%) | Mee |
---|---|---|---|---|
MMe | 88 | 88 | e.e. | [888] |
MMe | 88 | 88 | 88 | [888] |
MMe | 88 | 88 | e.e. | [888] |
MMe | 88 | 88 | e.e. | [888] |
Me-Me | 88 | 8 | e.e. | [888] |
MMM8MM=MM8 | 88 | 88 | e.e. | [888] |
eeeeeeeeee-8-ee | 88 | 88 | e.e. | [888] |
e e.e. = eee eeeeeeee.
Meeeeeeeeeee Meeeeeeee
Meeee ee Meeeee 8-Meeeeee-8-eeeeeeeeeeeeeeee 888; Meeeeee Meeeeeeee:[888]
MeMMMe (8.8 eeee) eee eee α-eeeeeeeeeee (8.8 eeee) eeee eeeee ee e eeeeeee eeee ee [MeMe(eeeee)] 8.88 eeee) ee e-MeMMe (8 eM) ee ee, eee eeee eee eeeeeee eee eeeeee ee ee eee eeee ee 888°M eee 8 eee, eeeeee Me8Me eee eeeee eeeeeeee. Mee eeeee, eeeeeeeeeee eeee eee eeeeeee eee 8–8 e ee eeeeee, eee eeee eeeeee ee ee. Mee. ee MeMMM8 eee eeeee ee eeeeee eee eeeeeeee eee eee eeeeeee eee eeeeeeee eeeeeee e eeeee eeeeee. Mee eeeeeee eeeee eee eeeeeeeee eeee eee eeeeeeee eee eee eeeeeee eeeee eee eeeeeeeee eeee Me8M (8 × 8 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeee (Me8MM8) eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeeee ee eee, eeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeeeeeee/Me8M 8:8 ee 8:8). Meeeeeeeeeeee ee eee ee ee eee eeeeeee eee eeeeeee eee ee MMMM eeeee e Meeeeeeee MM eeeeee eeee eeeeee/eMeMM 88:8 ee 88:8 (eeeeeeeee) eeeeeeee, eeee 8.8 eM·eee−8.
References
[103] | Meee-Meeeeee, M.; Meeeeeee, M. M., M. Mee. Meee., (8888) 88, 8888. |
[564] | Meeeeeeeeee, M., Mee. Meeee. Meee. Mee., (8888) 88, 8888. |
[565] | Meee, M.; Meeeeee, M.; Meeee, M.; Meeeee, M. M.; Meeeee, M. M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[566] | Meeeee, M.; Meeeeeeee, M. M. M.; Meeeeee, M.; eee eee Meee, M. M. M.; Meee, M. M., Meeeeeeeeeeeeee, (8888) 8, 8888. |
[567] | Meeeee, M. M., Mee. Meeee. (M. M.), (8888) 88, 888. |
[568] | Müeeeeee, M., Meeeeeeee, (8888), 888. |
[569] | Meeee, M., Meeeeeeeeee, (8888) 88, 8888. |
[570] | Müeeeeee, M., Me Meeeeeeeee Meeeeeee, Meeeeee, M.; Meeee, M., Mee.; Meeeee Meeeeeeeee Meeee: Mee Meee, (8888); e 888. |
[571] | Meeeeee, M.; Meeee, M. M., Meeeeeeee, (8888), 888. |
[572] | Meee, M.; Mee, M.; Meeee, M. M.; Meeeee, M. M., Meeeeeeeeee, (8888) 88, 8888. |
[573] | Meeeee, M.; Meeee, M., Meee. Mee. Meeee., (8888) 8, 888. |
[574] | Meeeee, M.; Meeeeee, M. M., Me., Meeeeeeeeee, (8888) 88, 8888. |
[575] | Meeeeee, M.; Meeeee, M. M., Meeee. Meeeee., (8888) 88, 888. |
[576] | Meeeeeeeee, M. M.; Meeeee, M., Meeeeeeee, (8888), 8. |
[577] | Mee, M. M., Me Meeeeee ee Meeeeeeee, (8888) Mee. 8, e 888. |
[578] | Meeeee, M.; Meeeeee, M.-M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[579] | Meeeee, M.; Meeeee, M.; Meee, M., M. Meee. Mee., Meee. Meeeee., (8888), 8888. |
[580] | Meeeeee, M.; Meeeee, M.; Meeee, M.; Meeeeeeee, M., Meee. Meee., (8888), 888. |
[581] | Me, M. M.; Me, M.; Meeee, M. M., Meee. Meee. Meee., (8888) 88, 888. |
[582] | Meeee, M. M.; Meeee, M. M., Meee. M. Meee., (8888) 88, 888. |
[583] | Meeeeeeee, M.; Meeeeeeee, M.; Meeee, M.; Meeee, M., M. Mee. Meee., (8888) 88, 888. |
[584] | Meeeee, M. M.; Meeeeeee, M. M., M. Mee. Meee., (8888) 88, 8888. |
[585] | Meee, M.; Meeee, M.; Meee, M.; Meeeee, M.; Meeeee, M.; Meeee, M.; Meee, M.; Meeeeeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[586] | Meeeeee, M.; Meee, M.; Meeeeeeeee, M.; Meee, M., Mee. Meee., (8888) 8, 888. |
[587] | Meeeeeeeee, M.; Meeeeeee, M., Meeeeeeee, (8888), 8888. |
[588] | Meeeeeeee, M.; Meeeeeeee, M.; Meeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[589] | Meee, M.; Meeeee, M. M.; Meeeeee, M. M., M. Me. Meee. Mee., (8888) 888, 8888. |
[590] | Meeeeeeeee, M. M.; Meee, M.; Meeeeeeee, M. M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[591] | Meeeee, M. M.; Meeeeeeeee, M.; Meeeee, M. M., M. Mee. Meee., (8888) 88, 8888. |
[592] | Meeeeee, M. M. M.; ee Meeeee, M. M. M., Meee-Mee. Mee. Meee., (8888) 8, 8. |
[593] | Meeeeeee, M.; Meeeeeee, M.; Meeeeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[594] | Meeeée, M. M.; Meeeeee, M.; Méeee-Meeeee, M., Meeeeeeeeee, (8888) 88, 8888. |
[595] | Meee, M.-M.; Mee, M. M.; Mee, M.; Mee, M.; Meee, M. M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[596] | Meee, M.; Meeeee, M.; Meeeee, M., Meeeeeeeeee: Meeeeeeee, (8888) 8, 888. |
[597] | Meeeeeee, M.; Meeeeeeee, M.; Meeeeeeeee, M., M. Mee. Meee., (8888) 88, 8888. |
[598] | Mee, M.; Meeeee, M.; Meeeee, M.; Meeeeeee, M.; Meeeeeeee, M., Meeeeeeeeee, (8888) 88, 8888. |
[599] | Mee, M.; Meeeeeeee, M., Meeeeeeeeee, (8888) 88, 8888. |
[600] | Meeeeee, M.; Meeeeeeeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[601] | Meee, M. M.; Meeeee, M.; Meeeeee, M.; Meee, M., M. Mee. Meee., (8888) 88, 88888. |
[602] | Meeee, M. M., Meeee. Meee., (8888) 888, 8888; Meeee. Meee. Mee. Me., (8888) 88, 8888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) 88/8e, 888.
- 8.Meeeee-Meee, (8888) 88/8e, 888.
- 8.Meeeee-Meee, (8888) M 88e, 8888.