288:
408:
138:
587:
195:
365:
have performed a systematic study of the reaction of methyl 2-(dimethylphosphono)acetate with various aldehydes. While each effect was small, they had a cumulative effect making it possible to modify the stereochemical outcome without modifying the structure of the phosphonate. They found greater
407:
287:
586:
321:(EWG) alpha to the phosphonate is necessary for the final elimination to occur. In the absence of an electron-withdrawing group, the final product is the β-hydroxyphosphonate
176:
but less basic. Likewise, phosphonate-stabilized carbanions can be alkylated. Unlike phosphonium ylides, the dialkylphosphate salt byproduct is easily removed by
1678:
571:-alkenes with excellent stereoselectivity. Using phosphonates with electron-withdrawing groups (trifluoroethyl) together with strongly dissociating conditions (
404:
The steric bulk of the phosphonate and electron-withdrawing groups plays a critical role in the reaction of α-branched phosphonates with aliphatic aldehydes.
137:
90:
1476:
1237:
594:
Ando has suggested that the use of electron-deficient phosphonates accelerates the elimination of the oxaphosphetane intermediates.
1521:
608:
1673:
572:
396:
In a separate study, it was found that bulky phosphonate and bulky electron-withdrawing groups enhance E-alkene selectivity.
613:
1451:
1456:
1668:
899:
533:, several procedures have been developed using milder bases. Masamune and Roush have developed mild conditions using
318:
83:
1647:
1627:
1074:
Simoni, D.; Rossi, M.; Rondanin, R.; Mazzali, A.; Baruchello, R.; Malagutti, C.; Roberti, M.; Invidiata, F. P.
180:
75:
1683:
1587:
334:
1582:
1461:
154:
1506:
1230:
998:
214:
504:)-alkenes from aromatic aldehydes are needed, the Still–Gennari modification (see below) can be used.
1516:
1496:
1433:
349:)-alkenes. In general, the more equilibration amongst intermediates, the higher the selectivity for (
311:
250:
1486:
1466:
1437:
1424:
1017:
1015:
Blanchette, M. A.; Choy, W.; Davis, J. T.; Essenfeld, A. P.; Masamune, S.; Roush, W. R.; Sakai, T.
1076:
1577:
1551:
1481:
1157:
1129:
816:
692:
673:
230:
17:
1617:
1541:
1531:
1501:
1442:
1176:
1149:
944:
917:
738:
711:
623:
618:
362:
165:
158:
112:
108:
59:
49:
1597:
1526:
1511:
1223:
1202:
1141:
1043:
980:
953:
926:
846:
828:
783:
720:
653:
534:
1637:
1607:
1536:
603:
580:
538:
281:
169:
150:
1632:
1622:
668:
564:
530:
310:
outcome of the initial carbanion addition and upon the ability of the intermediates to
307:
254:
146:
43:
1181:
743:
194:
1662:
1592:
1567:
1471:
1161:
971:
553:
203:
1642:
1572:
1546:
173:
1602:
912:
657:
644:
455:
116:
1612:
1428:
774:
576:
1153:
546:
468:
388:
207:
119:
1145:
411:
Example of the Horner–Wadsworth–Emmons reaction with branched phosphonates
1260:
493:
123:
1047:
984:
930:
832:
787:
724:
1345:
1311:
1277:
1061:
542:
380:
177:
1206:
957:
1446:
1396:
1379:
1362:
1328:
1294:
1246:
1130:"Still–Gennari Olefination and its Applications in Organic Synthesis"
549:
513:
431:
384:
330:
296:
131:
127:
193:
512:
The stereoselectivity of the Horner–Wadsworth–Emmons reaction of
198:
Deprotonation by base (B-) to generate the phosphonate carbanion
1219:
345:
The Horner–Wadsworth–Emmons reaction favours the formation of (
590:
The Still modification of the Horner–Wadsworth–Emmons reaction
329:. However, these β-hydroxyphosphonates can be transformed to
585:
406:
286:
136:
1215:
1174:
Patois, C.; Savignac, P.; About-Jaudet, E.; Collignon, N.
690:
Horner, L.; Hoffmann, H. M. R.; Wippel, H. G.; Klahre, G.
377:
Higher reaction temperatures (23 °C over −78 °C)
583:) nearly exclusive Z-alkene production can be achieved.
1180:, Coll. Vol. 9, p. 88 (1998); Vol. 73, p. 152 (1996). (
742:, Coll. Vol. 5, p. 547 (1973); Vol. 45, p. 44 (1965). (
291:
The mechanism of the Horner-Wadsworth-Emmons reaction
202:
The Horner–Wadsworth–Emmons reaction begins with the
1560:
1417:
1253:
567:and C. Gennari have developed conditions that give
370:)-stereoselectivity with the following conditions:
556:. Several other bases have been found effective.
1231:
1128:Janicki, Ignacy; Kiełbasiński, Piotr (2020).
172:, phosphonate-stabilized carbanions are more
8:
249:can interconvert with each other. The final
206:of the phosphonate to give the phosphonate
1238:
1224:
1216:
1059:Paterson, I.; Yeung, K.-S.; Smaill, J. B.
31:
153:using phosphonate-stabilized carbanions.
27:Variation on the Wittig chemical reaction
1406:
1402:
1389:
1385:
1372:
1368:
1355:
1351:
1338:
1334:
1321:
1317:
1304:
1300:
1287:
1283:
1270:
1266:
529:Since many substrates are not stable to
635:
496:aldehydes produce almost exclusively (
374:Increasing steric bulk of the aldehyde
280:, with the by-product being a dialkyl-
105:Horner–Wadsworth–Emmons (HWE) reaction
736:Wadsworth, W. S., Jr.; Emmons, W. D.
709:Wadsworth, W. S., Jr.; Emmons, W. D.
186:Several reviews have been published.
7:
1679:Carbon-carbon bond forming reactions
671:; Hoffmann, H. M. R.; Wippel, H. G.
141:The Horner–Wadsworth–Emmons reaction
942:Reichwein, J. F.; Pagenkopf, B. L.
217:of the carbanion onto the aldehyde
1134:Advanced Synthesis & Catalysis
969:Thompson, S. K.; Heathcock, C. H.
25:
35:Horner–Wadsworth–Emmons reaction
1492:Horner–Wadsworth–Emmons reaction
863:Bisceglia, J. A., Orelli, L. R.
844:Bisceglia, J. A., Orelli, L. R.
18:Horner-Wadsworth-Emmons reaction
897:Lefèbvre, G.; Seyden-Penne, J.
414:
233:. If R = H, then intermediates
161:further defined the reaction.
1:
1477:Corey–Winter olefin synthesis
1093:Blasdel, L. K.; Myers, A. G.
130:) to produce predominantly E-
486:
475:
462:
449:
438:
900:J. Chem Soc., Chem. Commun.
658:10.1002/0471264180.or025.02
1700:
1110:Still, W. C.; Gennari, C.
880:Larsen, R. O.; Aksnes, G.
609:Michaelis–Arbuzov reaction
541:. Rathke extended this to
319:electron-withdrawing group
306:is not dependent upon the
1648:Friedel-Crafts Alkylation
1522:Ramberg–Bäcklund reaction
1034:Rathke, M. W.; Nowak, M.
614:Michaelis–Becker reaction
525:Base sensitive substrates
97:
71:Organic Chemistry Portal
65:
34:
1452:Bamford–Stevens reaction
772:Boutagy, J.; Thomas, R.
1588:Oxymercuration reaction
1457:Barton–Kellogg reaction
996:Nagaoka, H.; Kishi, Y.
335:diisopropylcarbodiimide
1583:Electrophilic addition
1462:Boord olefin synthesis
1146:10.1002/adsc.201901591
755:Wadsworth, W. S., Jr.
591:
508:Olefination of ketones
412:
400:Trisubstituted alkenes
292:
221:(or ketone) producing
199:
142:
76:wittig-horner-reaction
1674:Olefination reactions
1507:Kauffmann olefination
915:; Kwiatkowski, G. T.
589:
410:
357:Disubstituted alkenes
290:
215:Nucleophilic addition
197:
149:published a modified
140:
47:William S. Wadsworth
1628:Diels–Alder reaction
1517:Peterson olefination
1497:Hydrazone iodination
1434:Dehydration reaction
854:, 2206–2230 (Review)
827:, 863–927. (Review,
500:)-alkenes. In case (
353:)-alkene formation.
295:The ratio of alkene
155:William S. Wadsworth
1487:Hofmann elimination
1467:Chugaev elimination
1425:Dehydrohalogenation
1112:Tetrahedron Letters
1048:10.1021/jo00215a004
1018:Tetrahedron Letters
985:10.1021/jo00297a076
931:10.1021/ja00975a057
833:10.1021/cr00094a007
807:, 729–817. (Review)
788:10.1021/cr60287a005
725:10.1021/ja01468a042
516:is poor to modest.
1669:Coupling reactions
1552:Cope rearrangement
1482:Grieco elimination
871:, 744–775 (Review)
801:Compr. Org. Synth.
782:, 87–99. (Review,
763:, 73–253. (Review)
592:
560:Still modification
413:
293:
241:and intermediates
231:rate-limiting step
200:
190:Reaction mechanism
166:phosphonium ylides
143:
1656:
1655:
1618:Hydrohalogenation
1542:Olefin metathesis
1532:Takai olefination
1502:Julia olefination
1443:Semihydrogenation
1207:10.1021/jo970057c
1177:Organic Syntheses
1140:(13): 2552–2596.
958:10.1021/ja027658s
945:J. Am. Chem. Soc.
918:J. Am. Chem. Soc.
882:Phosphorus Sulfur
739:Organic Syntheses
712:J. Am. Chem. Soc.
624:Tebbe olefination
619:Peterson reaction
491:
490:
341:Stereoselectivity
333:by reaction with
159:William D. Emmons
113:organic chemistry
109:chemical reaction
101:
100:
60:Coupling reaction
50:William D. Emmons
16:(Redirected from
1691:
1598:Cyclopropanation
1527:Shapiro reaction
1512:McMurry reaction
1409:
1392:
1375:
1358:
1341:
1324:
1307:
1290:
1273:
1240:
1233:
1226:
1217:
1210:
1191:
1185:
1172:
1166:
1165:
1125:
1119:
1108:
1102:
1091:
1085:
1072:
1066:
1057:
1051:
1032:
1026:
1013:
1007:
994:
988:
967:
961:
940:
934:
910:
904:
895:
889:
878:
872:
865:Curr. Org. Chem.
861:
855:
847:Curr. Org. Chem.
842:
836:
814:
808:
797:
791:
770:
764:
753:
747:
734:
728:
707:
701:
688:
682:
666:
660:
640:
535:lithium chloride
424:Ratio of alkenes
415:
93:
78:
32:
21:
1699:
1698:
1694:
1693:
1692:
1690:
1689:
1688:
1659:
1658:
1657:
1652:
1638:Dehydrogenation
1608:Dihydroxylation
1556:
1537:Wittig reaction
1413:
1408:
1404:
1400:
1391:
1387:
1383:
1374:
1370:
1366:
1357:
1353:
1349:
1340:
1336:
1332:
1323:
1319:
1315:
1306:
1302:
1298:
1289:
1285:
1281:
1272:
1268:
1264:
1249:
1244:
1214:
1213:
1192:
1188:
1173:
1169:
1127:
1126:
1122:
1109:
1105:
1092:
1088:
1073:
1069:
1058:
1054:
1033:
1029:
1014:
1010:
995:
991:
968:
964:
941:
937:
911:
907:
896:
892:
879:
875:
862:
858:
843:
839:
819:; Reitz, A. B.
817:B. E. Maryanoff
815:
811:
798:
794:
771:
767:
754:
750:
735:
731:
708:
704:
689:
685:
667:
663:
641:
637:
632:
604:Wittig reaction
600:
562:
527:
522:
510:
426:( E : Z )
425:
402:
395:
359:
343:
255:oxaphosphetanes
192:
170:Wittig reaction
164:In contrast to
151:Wittig reaction
89:
74:
48:
46:
28:
23:
22:
15:
12:
11:
5:
1697:
1695:
1687:
1686:
1684:Name reactions
1681:
1676:
1671:
1661:
1660:
1654:
1653:
1651:
1650:
1645:
1640:
1635:
1633:Wacker process
1630:
1625:
1623:Polymerization
1620:
1615:
1610:
1605:
1600:
1595:
1590:
1585:
1580:
1575:
1570:
1564:
1562:
1558:
1557:
1555:
1554:
1549:
1544:
1539:
1534:
1529:
1524:
1519:
1514:
1509:
1504:
1499:
1494:
1489:
1484:
1479:
1474:
1469:
1464:
1459:
1454:
1449:
1440:
1431:
1421:
1419:
1415:
1414:
1412:
1411:
1394:
1377:
1360:
1343:
1326:
1309:
1292:
1275:
1257:
1255:
1251:
1250:
1245:
1243:
1242:
1235:
1228:
1220:
1212:
1211:
1201:, 1934–1939. (
1186:
1167:
1120:
1103:
1086:
1067:
1052:
1042:, 2624–2626. (
1027:
1008:
989:
962:
935:
905:
903:1970, 1308–09.
890:
873:
856:
837:
809:
792:
765:
748:
729:
702:
683:
669:Leopold Horner
661:
642:Wadsworth, W.
634:
633:
631:
628:
627:
626:
621:
616:
611:
606:
599:
596:
565:W. Clark Still
561:
558:
531:sodium hydride
526:
523:
521:
518:
509:
506:
489:
488:
485:
482:
478:
477:
474:
471:
465:
464:
461:
458:
452:
451:
448:
445:
441:
440:
437:
434:
428:
427:
422:
419:
401:
398:
393:
392:
378:
375:
358:
355:
342:
339:
308:stereochemical
191:
188:
147:Leopold Horner
115:of stabilized
99:
98:
95:
94:
87:
80:
79:
72:
68:
67:
63:
62:
57:
56:Reaction type
53:
52:
44:Leopold Horner
41:
37:
36:
26:
24:
14:
13:
10:
9:
6:
4:
3:
2:
1696:
1685:
1682:
1680:
1677:
1675:
1672:
1670:
1667:
1666:
1664:
1649:
1646:
1644:
1641:
1639:
1636:
1634:
1631:
1629:
1626:
1624:
1621:
1619:
1616:
1614:
1611:
1609:
1606:
1604:
1601:
1599:
1596:
1594:
1593:Hydroboration
1591:
1589:
1586:
1584:
1581:
1579:
1576:
1574:
1571:
1569:
1568:Hydrogenation
1566:
1565:
1563:
1559:
1553:
1550:
1548:
1545:
1543:
1540:
1538:
1535:
1533:
1530:
1528:
1525:
1523:
1520:
1518:
1515:
1513:
1510:
1508:
1505:
1503:
1500:
1498:
1495:
1493:
1490:
1488:
1485:
1483:
1480:
1478:
1475:
1473:
1472:Cope reaction
1470:
1468:
1465:
1463:
1460:
1458:
1455:
1453:
1450:
1448:
1444:
1441:
1439:
1435:
1432:
1430:
1426:
1423:
1422:
1420:
1416:
1398:
1395:
1381:
1378:
1364:
1361:
1347:
1344:
1330:
1327:
1313:
1310:
1296:
1293:
1279:
1276:
1262:
1259:
1258:
1256:
1252:
1248:
1241:
1236:
1234:
1229:
1227:
1222:
1221:
1218:
1208:
1204:
1200:
1196:
1195:J. Org. Chem.
1190:
1187:
1183:
1179:
1178:
1171:
1168:
1163:
1159:
1155:
1151:
1147:
1143:
1139:
1135:
1131:
1124:
1121:
1117:
1113:
1107:
1104:
1100:
1096:
1090:
1087:
1083:
1079:
1078:
1071:
1068:
1064:
1063:
1056:
1053:
1049:
1045:
1041:
1037:
1036:J. Org. Chem.
1031:
1028:
1024:
1020:
1019:
1012:
1009:
1005:
1001:
1000:
993:
990:
986:
982:
978:
974:
973:
972:J. Org. Chem.
966:
963:
959:
955:
951:
947:
946:
939:
936:
932:
928:
924:
920:
919:
914:
909:
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902:
901:
894:
891:
887:
883:
877:
874:
870:
866:
860:
857:
853:
849:
848:
841:
838:
834:
830:
826:
822:
818:
813:
810:
806:
802:
799:Kelly, S. E.
796:
793:
789:
785:
781:
777:
776:
769:
766:
762:
758:
752:
749:
745:
741:
740:
733:
730:
726:
722:
718:
714:
713:
706:
703:
699:
695:
694:
687:
684:
680:
676:
675:
670:
665:
662:
659:
655:
651:
647:
646:
639:
636:
629:
625:
622:
620:
617:
615:
612:
610:
607:
605:
602:
601:
597:
595:
588:
584:
582:
578:
574:
570:
566:
559:
557:
555:
554:triethylamine
551:
548:
544:
540:
536:
532:
524:
519:
517:
515:
507:
505:
503:
499:
495:
483:
480:
479:
476:90 : 10
472:
470:
467:
466:
463:40 : 60
459:
457:
454:
453:
450:10 : 90
446:
443:
442:
435:
433:
430:
429:
423:
420:
417:
416:
409:
405:
399:
397:
390:
386:
382:
379:
376:
373:
372:
371:
369:
364:
361:Thompson and
356:
354:
352:
348:
340:
338:
336:
332:
328:
324:
320:
315:
313:
309:
305:
301:
298:
289:
285:
283:
279:
275:
271:
267:
263:
259:
256:
252:
248:
244:
240:
236:
232:
228:
224:
220:
216:
212:
209:
205:
204:deprotonation
196:
189:
187:
184:
182:
179:
175:
171:
167:
162:
160:
156:
152:
148:
139:
135:
133:
129:
125:
121:
118:
114:
110:
106:
96:
92:
88:
85:
82:
81:
77:
73:
70:
69:
64:
61:
58:
55:
54:
51:
45:
42:
39:
38:
33:
30:
19:
1643:Ene reaction
1573:Halogenation
1547:Ene reaction
1491:
1418:Preparations
1198:
1194:
1189:
1175:
1170:
1137:
1133:
1123:
1118:, 4405–4408.
1115:
1111:
1106:
1101:, 4281–4283.
1098:
1095:Org. Letters
1094:
1089:
1084:, 3765–3768.
1081:
1077:Org. Letters
1075:
1070:
1060:
1055:
1039:
1035:
1030:
1025:, 2183–2186.
1022:
1016:
1011:
1006:, 3873–3888.
1003:
997:
992:
979:, 3386–88. (
976:
970:
965:
952:, 1821–24. (
949:
943:
938:
925:, 5654–56. (
922:
916:
913:Corey, E. J.
908:
898:
893:
885:
881:
876:
868:
864:
859:
851:
845:
840:
824:
820:
812:
804:
800:
795:
779:
773:
768:
760:
756:
751:
737:
732:
716:
710:
705:
700:, 2499–2505.
697:
691:
686:
678:
672:
664:
649:
643:
638:
593:
568:
563:
528:
511:
501:
497:
492:
487:95 : 5
439:5 : 95
403:
394:
367:
360:
350:
346:
344:
326:
322:
316:
303:
299:
294:
277:
273:
269:
265:
261:
257:
246:
242:
238:
234:
226:
222:
218:
210:
201:
185:
174:nucleophilic
168:used in the
163:
144:
104:
102:
91:RXNO:0000056
86:ontology ID
66:Identifiers
40:Named after
29:
1603:Epoxidation
999:Tetrahedron
757:Org. React.
645:Org. React.
312:equilibrate
251:elimination
117:phosphonate
1663:Categories
1613:Ozonolysis
1429:haloalkane
1065:1993, 774.
888:, 218–219.
821:Chem. Rev.
775:Chem. Rev.
630:References
577:18-crown-6
520:Variations
484:Isopropyl
481:Isopropyl
181:extraction
120:carbanions
1578:Hydration
1561:Reactions
1193:Ando, K.
1162:216228029
1154:1615-4169
719:, 1733. (
547:magnesium
469:Isopropyl
363:Heathcock
282:phosphate
276:)-alkene
268:)-alkene
208:carbanion
145:In 1958,
124:aldehydes
681:, 61–63.
598:See also
494:Aromatic
111:used in
1438:alcohol
1346:Heptene
1312:Pentene
1278:Propene
1254:Alkenes
1247:Alkenes
1182:Article
1062:Synlett
744:Article
550:halides
543:lithium
514:ketones
444:Methyl
436:Methyl
331:alkenes
297:isomers
264:yield (
229:is the
178:aqueous
132:alkenes
128:ketones
1447:alkyne
1397:Decene
1380:Nonene
1363:Octene
1329:Hexene
1295:Butene
1261:Ethene
1197:1997,
1160:
1152:
1114:1983,
1097:2005,
1080:2000,
1038:1985,
1021:1984,
1002:1981,
975:1990,
948:2003,
921:1966,
884:1983,
867:2015,
850:2012,
823:1989,
803:1991,
778:1974,
759:1977,
715:1961,
696:1959,
677:1958,
652:, 73.
648:1977,
473:Ethyl
460:Ethyl
447:Ethyl
432:Methyl
1445:from
1436:from
1427:from
1158:S2CID
573:KHMDS
552:with
456:Ethyl
391:salts
387:>
383:>
272:and (
122:with
107:is a
1150:ISSN
693:Ber.
674:Ber.
575:and
537:and
325:and
317:The
302:and
260:and
245:and
237:and
157:and
126:(or
103:The
1203:doi
1142:doi
1138:362
1044:doi
981:doi
954:doi
950:125
927:doi
829:doi
784:doi
721:doi
654:doi
581:THF
579:in
545:or
539:DBU
253:of
225:or
84:RSC
1665::
1407:20
1403:10
1390:18
1373:16
1356:14
1339:12
1322:10
1199:62
1156:.
1148:.
1136:.
1132:.
1116:24
1040:50
1023:25
1004:37
977:55
923:88
886:15
869:19
852:16
825:89
780:74
761:25
717:83
698:92
679:91
650:25
421:R
418:R
385:Na
381:Li
337:.
327:3b
323:3a
314:.
284:.
262:4b
258:4a
247:4b
243:3b
239:4a
235:3a
227:3b
223:3a
213:.
183:.
134:.
1410:)
1405:H
1401:C
1399:(
1393:)
1388:H
1386:9
1384:C
1382:(
1376:)
1371:H
1369:8
1367:C
1365:(
1359:)
1354:H
1352:7
1350:C
1348:(
1342:)
1337:H
1335:6
1333:C
1331:(
1325:)
1320:H
1318:5
1316:C
1314:(
1308:)
1305:8
1303:H
1301:4
1299:C
1297:(
1291:)
1288:6
1286:H
1284:3
1282:C
1280:(
1274:)
1271:4
1269:H
1267:2
1265:C
1263:(
1239:e
1232:t
1225:v
1209:)
1205::
1184:)
1164:.
1144::
1099:7
1082:2
1050:)
1046::
987:)
983::
960:)
956::
933:)
929::
835:)
831::
805:1
790:)
786::
746:)
727:)
723::
656::
569:Z
502:Z
498:E
389:K
368:E
366:(
351:E
347:E
304:6
300:5
278:6
274:Z
270:5
266:E
219:2
211:1
20:)
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