292:
279:
286:
273:
131:
386:
355:
142:
reagent, also called a 'Reformatsky enolate', is prepared by treating an alpha-halo ester with zinc dust. Reformatsky enolates are less reactive than lithium enolates or
Grignard reagents and hence nucleophilic addition to the ester group does not occur. The reaction was discovered by
261:. Note that, in contrast to lithium and boron enolates, which have the metal(loid)s exclusively bond to oxygen, the zinc enolate moiety in the Reformatsky reagents have zinc atoms that are simultaneously O- and C-bound and can therefore be described as "
245:-butyl bromozincacetate and ethyl bromozincacetate have been determined. Both form cyclic eight-membered dimers in the solid state, but differ in stereochemistry: the eight-membered ring in the ethyl derivative adopts a tub-shaped conformation and has
949:
Imamoto, Tsuneo; Kusumoto, Tetsuo; Tawarayama, Yoshinori; Sugiura, Yasushi; Mita, Takeshi; Hatanaka, Yasuo; Yokoyama, Masataka (1984). "Carbon-carbon bond-forming reactions using cerium metal or organocerium(III) reagents".
1095:
Fukuzawa, Shin-Ichi; Fujinami, Tatsuo; Sakai, Shizuyoshi (1985). "Carbon–carbon bond formation between α-halogenoketones and aldehydes promoted by cerium(III) iodide or cerium(III) chloride–sodium iodide".
692:
Liu, Xuan-Yu; Li, Xiang-Rui; Zhang, Chen; Chu, Xue-Qiang; Rao, Weidong; Loh, Teck-Peng; Shen, Zhi-Liang (2019). "Iron(0)-Mediated
Reformatsky Reaction for the Synthesis of β-Hydroxyl Carbonyl Compounds".
1197:
Miki, S.; Nakamoto, K.; Kawakami, J.; Handa, S.; Nuwa, S. (2008). "The First
Isolation of Crystalline Ethyl Bromozincacetate, Typical Reformatsky Reagent: Crystal Structure and Convenient Preparation".
580:
Sato, Toshio; Itoh, Toshiyuki; Fujisawa, Tamotsu (1982). "Facile synthesis of β-ketoesters by a coupling reaction of the
Reformatsky reagent with acyl chlorides catalyzed by a palladium complex".
1008:
Molander, Gary A.; Etter, Jeffrey B. (1987). "Lanthanides in organic synthesis. 8. 1.3-Asymmetric induction in intramolecular
Reformatskii-type reactions promoted by samarium diiodide".
979:
Tabuchi, Takanori; Kawamura, Kisa; Inanaga, Junji; Yamaguchi, Masaru (1986). "Preparation of medium- and large-ring lactones. SmI2-induced cyclization of ω-(α-bromoacyloxy) aldehydes".
1066:
Ishihara, Takashi; Yamanaka, Tohru; Ando, Teiichi (1984). "New low-valent titanium catalyzed reaction of chlorodifluoromethyl ketones leading to α,α-difluorinated β-hydroxy ketones".
796:
Kagoshima, Hirotaka; Hashimoto, Yukihiko; Oguro, Dai; Saigo, Kazuhiko (1998). "An
Activated Germanium Metal-Promoted, Highly Diastereoselective Reformatsky Reaction".
738:
Orsini, Fulvia; Pelizzoni, Francesca; Pulici, Maurizio; Vallarino, Lidia M. (1994). "A cobalt-phosphine complex as mediator in the formation of carbon-carbon bonds".
1156:
Dekker, J.; Budzelaar, P. H. M.; Boersma, J.; van der Kerk, G. J. M. & Spek, A. J. (1984). "The Nature of the
Reformatsky Reagent. Crystal Structure of (BrZnCH
862:
Chao, Li-Chung; Rieke, Reuben D. (1975). "Activated metals. IX. New reformatsky reagent involving activated indium for the preparation of β-hydroxy esters".
636:
Stamm, H.; Steudle, H. (1979). "Nitrone—XI Isoxazolidin-verbindungen—VIII : N-substituierte 5-isoxazolidinone durch reformatzky-reaktion mit nitronen".
918:
Yanagisawa, Akira; Takahashi, Hiroshi; Arai, Takayoshi (2004). "Reactive barium-promoted
Reformatsky-type reaction of α-chloroketones with aldehydes".
833:
Burkhardt, Elizabeth R.; Rieke, Reuben D. (1985). "The direct preparation of organocadmium compounds from highly reactive cadmium metal powders".
1037:
Dubois, Jacques-Emile; Axiotis, Georges; Bertounesque, Emmanuel (1985). "Chromium (II) chloride : a new reagent for cross-aldol reactions".
1281:
79:
226:
767:
Inaba, Shin-ichi; Rieke, Reuben D. (1985). "Reformatsky type additions of haloacetonitriles to aldehydes mediated by metallic nickel".
1230:
1010:
609:
385:
891:
Araki, Shuki; Ito, Hirokazu; Butsugan, Yasuo (1988). "Synthesis of β-Hydroxyesters by
Reformatsky Reaction Using Indium Metal".
17:
130:
663:
Moriwake, Tosio (1966). "The
Reformatsky Reaction. I. Condensation of Ketones and t-Butyl Bromoacetate by Magnesium".
1286:
507:
335:. A rearrangement occurs in which zinc switches to the aldehyde or ketone oxygen and a carbon-carbon bond is formed
952:
864:
835:
798:
740:
665:
415:
331:. The oxygen on an aldehyde or ketone coordinates to the zinc to form the six-member chair like transition state
1119:
Parrish, J. D.; Shelton, Daniel R.; Little, R. Daniel (2003). "Titanocene(III)-Promoted Reformatsky Additions".
291:
153:
In addition to aldehydes and ketones, it has also been shown that the Reformatsky enolate is able to react with
544:
64:
278:
1276:
1271:
72:
285:
262:
1291:
272:
1155:
218:
214:
109:
467:
Reformatsky, S. (1890). "Action of zinc and ethyl chloroacetate on ketones and aldehydes".
409:
8:
1039:
981:
769:
210:
257:-butyl derivative, the ring is in a chair form and the bromo groups and THF ligands are
720:
607:
Gilman, Henry; Speeter, Merrill (1943). "The Reformatsky Reaction with Benzalaniline".
321:
222:
144:
38:
1052:
994:
782:
1247:
1138:
1068:
931:
815:
724:
712:
649:
540:
503:
48:
1239:
1207:
1179:
1130:
1101:
1077:
1048:
1019:
990:
961:
923:
900:
873:
844:
807:
778:
749:
704:
674:
645:
618:
589:
532:
495:
449:
105:
1170:
1121:
695:
404:
238:
166:
97:
708:
536:
499:
399:
375:
154:
904:
453:
1265:
209:. Additionally, metal salts are also applicable in place of metals, notably
1251:
1211:
1142:
935:
819:
716:
1228:
Lambert, T. H.; Danishefsky, S. J. (2006). "Total Synthesis of UCS1025A".
320:
Zinc metal is inserted into the carbon-halogen bond of the α-haloester by
1196:
1105:
1081:
593:
1183:
1023:
965:
877:
848:
753:
678:
622:
139:
1243:
1134:
811:
927:
190:
174:
437:
371:
327:. This compound dimerizes and rearranges to form two zinc enolates
170:
162:
112:
173:. Moreover, metals other than zinc have also been used, including
379:
194:
1227:
948:
438:"Neue Synthese zweiatomiger einbasischer Säuren aus den Ketonen"
978:
367:
206:
202:
198:
186:
182:
158:
116:
737:
568:
Strategic Applications of Named Reactions in Organic Synthesis
120:
795:
347:
removes zinc to yield zinc(II) salts and a β-hydroxy-ester
178:
124:
354:
1036:
1098:
Journal of the Chemical Society, Chemical Communications
917:
1094:
1118:
1065:
486:Shriner, R. L. (1942). "The Reformatsky Reaction".
523:Rathke, M. W. (1975). "The Reformatsky Reaction".
1263:
890:
579:
366:In one variation of the Reformatsky reaction an
466:
435:
832:
485:
442:Berichte der Deutschen Chemischen Gesellschaft
1007:
691:
606:
522:
635:
232:
1223:
1221:
766:
389:Reformatsky reaction Danishefsky variation
861:
1231:Journal of the American Chemical Society
1011:Journal of the American Chemical Society
662:
610:Journal of the American Chemical Society
1218:
562:
560:
558:
556:
14:
1264:
942:
241:complexes of the Reformatsky reagents
315:
1282:Carbon-carbon bond forming reactions
685:
553:
24:
384:
353:
150:Some reviews have been published.
129:
25:
1303:
953:The Journal of Organic Chemistry
865:The Journal of Organic Chemistry
836:The Journal of Organic Chemistry
799:The Journal of Organic Chemistry
741:The Journal of Organic Chemistry
666:The Journal of Organic Chemistry
414:Example use in total synthesis:
290:
284:
277:
271:
1190:
1149:
1112:
1088:
1059:
1030:
1001:
972:
911:
884:
855:
826:
789:
760:
731:
416:Mukaiyama Taxol total synthesis
656:
629:
600:
573:
516:
479:
460:
429:
237:The crystal structures of the
221:, cerium(III) halides such as
145:Sergey Nikolaevich Reformatsky
13:
1:
1053:10.1016/S0040-4039(00)98737-9
995:10.1016/S0040-4039(00)83907-6
783:10.1016/S0040-4039(00)61867-1
570:; Elsevier: Burlington, 2005.
422:
361:
308:-butyl bromozincacetate dimer
650:10.1016/0040-4020(79)87010-6
300:ethyl bromozincacetate dimer
253:THF ligands, whereas in the
7:
709:10.1021/acs.orglett.9b01999
537:10.1002/0471264180.or022.04
500:10.1002/0471264180.or001.01
393:
10:
1308:
127:to form β-hydroxy-esters:
905:10.1080/00397918808064009
454:10.1002/cber.188702001268
86:
60:Organic Chemistry Portal
54:
29:
1287:Organometallic chemistry
893:Synthetic Communications
469:J. Russ. Phys. Chem. Soc
436:Reformatsky, S. (1887).
233:Structure of the reagent
227:titanocene(III) chloride
134:The Reformatsky reaction
920:Chemical Communications
1212:10.1055/s-2008-1032023
390:
358:
135:
566:Kurti, L.; Czako, B.
418:(B ring construction)
388:
357:
219:titanium(II) chloride
215:chromium(II) chloride
133:
102:Reformatskii reaction
30:Reformatsky reaction
18:Reformatskii reaction
1106:10.1039/C39850000777
1082:10.1246/cl.1984.1165
594:10.1246/cl.1982.1559
410:Claisen condensation
94:Reformatsky reaction
65:reformatsky-reaction
1184:10.1021/om00087a015
1040:Tetrahedron Letters
1024:10.1021/ja00255a076
982:Tetrahedron Letters
966:10.1021/jo00195a006
878:10.1021/jo00903a031
849:10.1021/jo00203a036
770:Tetrahedron Letters
754:10.1021/jo00080a001
679:10.1021/jo01341a524
623:10.1021/ja01251a503
370:is coupled with an
211:samarium(II) iodide
1277:Addition reactions
1272:Coupling reactions
391:
359:
322:oxidative addition
316:Reaction mechanism
223:cerium(III) iodide
136:
39:Sergey Reformatsky
1244:10.1021/ja0574567
1135:10.1021/ol035269c
1129:(20): 3615–3617.
1069:Chemistry Letters
1047:(36): 4371–4372.
1018:(21): 6556–6558.
989:(33): 3889–3890.
960:(21): 3904–3912.
872:(15): 2253–2255.
812:10.1021/jo971672j
703:(15): 5873–5878.
617:(11): 2255–2256.
588:(10): 1559–1560.
582:Chemistry Letters
525:Organic Reactions
488:Organic Reactions
313:
312:
309:
301:
249:bromo groups and
90:
89:
49:Coupling reaction
16:(Redirected from
1299:
1256:
1255:
1225:
1216:
1215:
1194:
1188:
1187:
1178:(3): 1403–1407.
1153:
1147:
1146:
1116:
1110:
1109:
1092:
1086:
1085:
1076:(7): 1165–1168.
1063:
1057:
1056:
1034:
1028:
1027:
1005:
999:
998:
976:
970:
969:
946:
940:
939:
928:10.1039/B314752P
915:
909:
908:
888:
882:
881:
859:
853:
852:
830:
824:
823:
793:
787:
786:
764:
758:
757:
735:
729:
728:
689:
683:
682:
660:
654:
653:
633:
627:
626:
604:
598:
597:
577:
571:
564:
551:
550:
520:
514:
513:
483:
477:
476:
464:
458:
457:
448:(1): 1210–1211.
433:
382:at -78 °C.
304:
299:
294:
288:
281:
275:
268:
267:
106:organic reaction
82:
67:
27:
26:
21:
1307:
1306:
1302:
1301:
1300:
1298:
1297:
1296:
1262:
1261:
1260:
1259:
1226:
1219:
1195:
1191:
1171:Organometallics
1167:
1159:
1154:
1150:
1122:Organic Letters
1117:
1113:
1100:(12): 777–778.
1093:
1089:
1064:
1060:
1035:
1031:
1006:
1002:
977:
973:
947:
943:
916:
912:
889:
885:
860:
856:
831:
827:
794:
790:
765:
761:
736:
732:
696:Organic Letters
690:
686:
661:
657:
634:
630:
605:
601:
578:
574:
565:
554:
547:
521:
517:
510:
484:
480:
465:
461:
434:
430:
425:
405:Blaise reaction
396:
364:
318:
289:
276:
235:
167:Blaise reaction
123:using metallic
78:
63:
23:
22:
15:
12:
11:
5:
1305:
1295:
1294:
1292:Name reactions
1289:
1284:
1279:
1274:
1258:
1257:
1238:(2): 426–427.
1217:
1206:(3): 409–412.
1189:
1165:
1157:
1148:
1111:
1087:
1058:
1029:
1000:
971:
941:
922:(5): 580–581.
910:
899:(4): 453–458.
883:
854:
843:(3): 416–417.
825:
806:(3): 691–697.
788:
777:(2): 155–156.
759:
730:
684:
673:(3): 983–985.
655:
644:(5): 647–650.
628:
599:
572:
552:
545:
515:
508:
478:
459:
427:
426:
424:
421:
420:
419:
412:
407:
402:
400:Aldol reaction
395:
392:
376:triethylborane
363:
360:
339:. Acid workup
317:
314:
311:
310:
302:
296:
295:
282:
263:organometallic
234:
231:
155:acid chlorides
98:transliterated
88:
87:
84:
83:
76:
69:
68:
61:
57:
56:
52:
51:
46:
45:Reaction type
42:
41:
36:
32:
31:
9:
6:
4:
3:
2:
1304:
1293:
1290:
1288:
1285:
1283:
1280:
1278:
1275:
1273:
1270:
1269:
1267:
1253:
1249:
1245:
1241:
1237:
1233:
1232:
1224:
1222:
1213:
1209:
1205:
1201:
1193:
1185:
1181:
1177:
1173:
1172:
1163:
1152:
1144:
1140:
1136:
1132:
1128:
1124:
1123:
1115:
1107:
1103:
1099:
1091:
1083:
1079:
1075:
1071:
1070:
1062:
1054:
1050:
1046:
1042:
1041:
1033:
1025:
1021:
1017:
1013:
1012:
1004:
996:
992:
988:
984:
983:
975:
967:
963:
959:
955:
954:
945:
937:
933:
929:
925:
921:
914:
906:
902:
898:
894:
887:
879:
875:
871:
867:
866:
858:
850:
846:
842:
838:
837:
829:
821:
817:
813:
809:
805:
801:
800:
792:
784:
780:
776:
772:
771:
763:
755:
751:
747:
743:
742:
734:
726:
722:
718:
714:
710:
706:
702:
698:
697:
688:
680:
676:
672:
668:
667:
659:
651:
647:
643:
639:
632:
624:
620:
616:
612:
611:
603:
595:
591:
587:
583:
576:
569:
563:
561:
559:
557:
548:
542:
538:
534:
530:
526:
519:
511:
509:9780471264187
505:
501:
497:
493:
489:
482:
474:
470:
463:
455:
451:
447:
443:
439:
432:
428:
417:
413:
411:
408:
406:
403:
401:
398:
397:
387:
383:
381:
377:
373:
369:
356:
352:
350:
346:
342:
338:
334:
330:
326:
323:
307:
303:
298:
297:
293:
287:
283:
280:
274:
270:
269:
266:
264:
260:
256:
252:
248:
244:
240:
230:
228:
224:
220:
216:
212:
208:
204:
200:
196:
192:
188:
184:
180:
176:
172:
168:
164:
160:
156:
151:
148:
146:
141:
132:
128:
126:
122:
118:
114:
111:
107:
103:
99:
95:
85:
81:
77:
74:
71:
70:
66:
62:
59:
58:
53:
50:
47:
44:
43:
40:
37:
34:
33:
28:
19:
1235:
1229:
1203:
1199:
1192:
1175:
1169:
1161:
1151:
1126:
1120:
1114:
1097:
1090:
1073:
1067:
1061:
1044:
1038:
1032:
1015:
1009:
1003:
986:
980:
974:
957:
951:
944:
919:
913:
896:
892:
886:
869:
863:
857:
840:
834:
828:
803:
797:
791:
774:
768:
762:
745:
739:
733:
700:
694:
687:
670:
664:
658:
641:
637:
631:
614:
608:
602:
585:
581:
575:
567:
528:
524:
518:
491:
487:
481:
472:
468:
462:
445:
441:
431:
365:
348:
344:
340:
336:
332:
328:
324:
319:
305:
258:
254:
250:
246:
242:
236:
152:
149:
137:
119:with α-halo
101:
93:
91:
80:RXNO:0000036
75:ontology ID
55:Identifiers
35:Named after
638:Tetrahedron
531:: 423–460.
96:(sometimes
1266:Categories
1164:-Bu · THF)
748:(1): 1–3.
546:0471264180
423:References
368:iodolactam
362:Variations
140:organozinc
1200:Synthesis
725:197541600
191:germanium
175:magnesium
113:aldehydes
110:condenses
1252:16402826
1143:14507186
936:14973617
820:11672062
717:31318222
494:: 1–37.
394:See also
372:aldehyde
171:nitrones
163:nitriles
104:) is an
380:toluene
195:cadmium
169:), and
117:ketones
1250:
1141:
934:
818:
723:
715:
543:
506:
225:, and
207:cerium
205:, and
203:barium
199:indium
187:nickel
183:cobalt
159:imines
121:esters
108:which
721:S2CID
475:: 44.
374:with
259:trans
165:(see
1248:PMID
1204:2008
1160:COO-
1139:PMID
932:PMID
816:PMID
713:PMID
541:ISBN
504:ISBN
306:tert
255:tert
243:tert
179:iron
138:The
125:zinc
92:The
1240:doi
1236:128
1208:doi
1180:doi
1168:".
1131:doi
1102:doi
1078:doi
1049:doi
1020:doi
1016:109
991:doi
962:doi
924:doi
901:doi
874:doi
845:doi
808:doi
779:doi
750:doi
705:doi
675:doi
646:doi
619:doi
590:doi
533:doi
496:doi
450:doi
378:in
265:".
251:cis
247:cis
239:THF
157:,
115:or
100:as
73:RSC
1268::
1246:.
1234:.
1220:^
1202:.
1174:.
1137:.
1125:.
1074:13
1072:.
1045:26
1043:.
1014:.
987:27
985:.
958:49
956:.
930:.
897:18
895:.
870:40
868:.
841:50
839:.
814:.
804:63
802:.
775:26
773:.
746:59
744:.
719:.
711:.
701:21
699:.
671:31
669:.
642:35
640:.
615:65
613:.
586:11
584:.
555:^
539:.
529:22
527:.
502:.
490:.
473:22
471:.
446:20
444:.
440:.
351:.
229:.
217:,
213:,
201:,
197:,
193:,
189:,
185:,
181:,
177:,
161:,
147:.
1254:.
1242::
1214:.
1210::
1186:.
1182::
1176:9
1166:2
1162:t
1158:2
1145:.
1133::
1127:5
1108:.
1104::
1084:.
1080::
1055:.
1051::
1026:.
1022::
997:.
993::
968:.
964::
938:.
926::
907:.
903::
880:.
876::
851:.
847::
822:.
810::
785:.
781::
756:.
752::
727:.
707::
681:.
677::
652:.
648::
625:.
621::
596:.
592::
549:.
535::
512:.
498::
492:1
456:.
452::
349:7
345:6
343:,
341:5
337:4
333:3
329:2
325:1
20:)
Text is available under the Creative Commons Attribution-ShareAlike License. Additional terms may apply.
