203:
109:
622:
311:
425:
391:
355:
589:
496:
469:
523:
546:
711:
Oppenauer, R. V. (1937). "Eine
Methode der Dehydrierung von Sekundären Alkoholen zu Ketonen. I. Zur Herstellung von Sterinketonen und Sexualhormonen" [Dehydration of secondary alcohols to ketones. I. Preparation of sterol ketones and sex hormones].
1012:
Almeida, Maria L.S.; Kočovský, Paval; Bäckvall, Jan-E. (1996). "Ruthenium-Catalyzed
Oppenauer-Type Oxidation of 3β-Hydroxy Steroids. A Highly Efficient Entry into the Steroidal Hormones with 4-En-3-one Functionality".
175:
due to its use of relatively mild and non-toxic reagents (e.g. the reaction is run in acetone/benzene mixtures). The
Oppenauer oxidation is commonly used in various industrial processes such as the synthesis of
252:
An advantage of the
Oppenauer oxidation is its use of relatively inexpensive and non-toxic reagents. Reaction conditions are mild and gentle since the substrates are generally heated in acetone/
772:
Otvos, L.; Gruber, L.; Meisel-Agoston, J. (1965). "The
Meerwein-Ponndorf-Verley-Oppenauer. Investigation of the reaction mechanism with radiocarbon. Racemization of secondary alcohols".
83:
155:
products. The
Oppenauer oxidation is still used for the oxidation of acid labile substrates. The method has been largely displaced by oxidation methods based on
951:
Stéphane Caron; Robert W. Dugger; Sally Gut
Ruggeri; John A. Ragan & David H. Brown Ripin (2006). "Large-Scale Oxidations in the Pharmaceutical Industry".
877:
Ooi, T.; Otsuka, H.; Miura, T.; Ichikawa, H.; Maruoka, K. (2002). "Practical
Oppenauer (OPP) oxidation of alcohols with a modified aluminum catalyst".
373:
have been also reported. For example, a highly active aluminium catalyst was reported by
Maruoka and co-workers which was utilized in the oxidation of
345:
to quininone, as the traditional aluminium catalytic system failed to oxidize quinine due to the complex formed by coordination of the Lewis-basic
147:. Though primary alcohols can be oxidized under Oppenauer conditions, primary alcohols are seldom oxidized by this method due to the competing
66:
117:
914:
Graves, C. R.; Zeng, B. S.; Nguyen, S. T. (2006). "Efficient and
Selective Al-Catalyzed Alcohol Oxidation via Oppenauer Chemistry".
1084:
916:
333:, is used when certain alcohol groups do not oxidize under the standard Oppenauer reaction conditions. For example, Woodward used
108:
805:
202:
1177:
621:
577:
1140:
Reich, Richard; Keana, John F. W. (1972). "Oppenauer Oxidations Using 1-Methyl-4-Piperidone as the Hydride Acceptor".
310:
1172:
1078:
Milas, N. A.; Grossi, F. X.; Penner, S. E.; Kahn, S. (1948). "The Synthesis of 1--3-Methyl-1,3,5-Octatrien-7-One (C
1049:
Eignerova, L.; Kasal, A. (1976). "Intramolecular hydride shift in Oppenauer oxidation of some dihydroxy steroids".
685:
424:
495:
390:
588:
256:
mixtures. Another advantage of the Oppenauer oxidation which makes it unique to other oxidation methods such as
1111:
Reich, R.; Keana, J. F. W. (1972). "Oppenauer Oxidations Using 1-Methyl-4-Piperidone as the Hydride Acceptor".
996:
650:
51:
655:
232:
alcohol are bound to the aluminium. The acetone is coordinated to the aluminium which activates it for the
236:
transfer from the alkoxide. The aluminium-catalyzed hydride shift from the α-carbon of the alcohol to the
139:
is highly selective for secondary alcohols and does not oxidize other sensitive functional groups such as
675:
522:
261:
468:
714:
660:
88:
59:
640:
305:
acceptor. This reaction is useful in that it affords a one-step preparation of Δ 4,6-3-ketosteroids.
257:
172:
160:
614:
solvents. Another general side reaction is the migration of the double bond during the oxidation of
509:
derivatives. For example, an efficient catalytic version of the Oppenauer oxidation which employs a
354:
1113:
329:
for the aluminium alkoxide. The Woodward modification of the Oppenauer oxidation, also called the
1182:
670:
545:
444:
334:
326:
121:
35:
603:
229:
225:
950:
129:
8:
408:
98:
565:
401:
213:
164:
148:
744:(1944). "Reduction with Aluminum Alkoxides (The Meerwein-Ponndorf-Verley Reduction)".
1031:
992:
969:
933:
896:
851:
823:
801:
635:
599:
293:
In the Wettstein-Oppenauer reaction, discovered by Wettstein in 1945, Δ 5–3β-hydroxy
94:
1149:
1122:
1093:
1060:
1023:
961:
925:
888:
859:
831:
754:
723:
561:
265:
241:
879:
741:
665:
645:
615:
277:
273:
168:
758:
264:
is that secondary alcohols are oxidized much faster than primary alcohols, thus
220:
to form a complex (3), which then, in the second step, gets deprotonated by an
1153:
1126:
1166:
1015:
727:
681:
1051:
1035:
973:
937:
900:
487:
483:
338:
298:
156:
821:
Mandell, L. (1955). "The Mechanism of the Wettstein-Oppenauer Oxidation".
513:
catalyst has been developed for the oxidation of 5-unsaturated 3β-hydroxy
1064:
746:
505:
A slight variation of the Oppenauer oxidation is also used to synthesize
1097:
863:
835:
953:
849:
Woodward, R. B.; Wendler, N. L.; Brutschy, F. J. (1945). "Quininone1".
412:
1027:
965:
929:
892:
771:
611:
510:
456:
440:
382:
217:
136:
607:
580:
573:
569:
533:
479:
448:
405:
370:
346:
302:
269:
237:
221:
185:
152:
244:(8). The desired ketone (9) is formed after the hydride transfer.
610:
products with no α-hydrogen, but this can be prevented by use of
514:
506:
460:
452:
416:
378:
374:
342:
294:
253:
233:
189:
181:
177:
144:
125:
102:
798:
Strategic Applications of Named Reactions in Organic Synthesis
691:
228:(5). In the third step, both the oxidant acetone (7) and the
140:
268:
can be achieved. Furthermore, there is no over oxidation of
537:
765:
572:
product, which have α-hydrogens to form either β-hydroxy
560:
A common side-reaction of the Oppenauer oxidation is the
532:
The Oppenauer oxidation is also used in the synthesis of
411:
is used as the oxidant, for example, in the oxidation of
1104:
1011:
848:
876:
1077:
1005:
1042:
989:
Medicinal Natural Products: A Biosynthetic Approach
795:
478:The Oppenauer oxidation is also used to synthesize
325:In the Woodward modification, Woodward substituted
1071:
814:
276:as opposed to another oxidation methods such the
1164:
913:
991:(2nd ed.). Wiley & Sons. p. 243.
288:
240:carbon of acetone proceeds over a six-membered
1048:
791:
789:
787:
625:Oppenauer oxidation of a steroid derivative.
517:to the corresponding 4-en-3-one derivative.
820:
439:The Oppenauer oxidation is used to prepare
1139:
1110:
486:is prepared by the Oppenauer oxidation of
459:is prepared by the Oppenauer oxidation of
381:(a member of a family of chemicals called
297:are oxidized to Δ 4,6-3-ketosteroids with
784:
734:
710:
434:
1085:Journal of the American Chemical Society
917:Journal of the American Chemical Society
400:In another modification the catalyst is
320:
842:
1165:
986:
944:
870:
526:An Oppenauer oxidation of pregnenolone
499:An Oppenauer oxidation of pregnenolone
364:
740:
216:, the alcohol (1) coordinates to the
93:, is a gentle method for selectively
369:Several modified aluminium alkoxide
796:Corey, E.J; Nicolaou, K.C. (2005).
428:An Oppenauer oxidation modification
112:Oppenauer oxidation reaction scheme
13:
620:
592:An Oppenauer oxidation of aldehyde
587:
544:
521:
494:
467:
423:
389:
353:
309:
201:
118:Meerwein–Ponndorf–Verley reduction
107:
14:
1194:
555:
472:An Oppenauer oxidation of codeine
394:An Oppenauer oxidation modication
283:
224:ion (4) to generate an alkoxide
1133:
980:
120:. The alcohol is oxidized with
907:
704:
549:An Oppenauer oxidation of diol
1:
698:
247:
206:Oppenauer oxidation mechanism
116:The reaction is the opposite
385:) in excellent yield (94%).
331:Oppenauer–Woodward oxidation
314:Wettstein-Oppenauer reaction
289:Wettstein-Oppenauer reaction
195:
7:
1178:Organic oxidation reactions
759:10.1002/0471264180.or002.05
629:
10:
1199:
774:Acta Chim. Acad. Sci. Hung
715:Recl. Trav. Chim. Pays-Bas
661:Albright-Goldman oxidation
651:Pfitzner–Moffatt oxidation
212:In the first step of this
1154:10.1080/00397917208061988
1127:10.1080/00397917208061988
641:Pyridinium chlorochromate
349:to the aluminium centre.
258:pyridinium chlorochromate
161:pyridinium chlorochromate
132:toward the product side.
73:
47:Organic Chemistry Portal
41:
18:
1142:Synthetic Communications
1114:Synthetic Communications
728:10.1002/recl.19370560206
656:Parikh–Doering oxidation
27:Rupert Viktor Oppenauer
1173:Organic redox reactions
676:Dess–Martin periodinane
445:pharmaceutical industry
335:potassium tert-butoxide
327:potassium tert-butoxide
262:Dess–Martin periodinane
84:Rupert Viktor Oppenauer
626:
593:
550:
527:
500:
473:
435:Synthetic applications
429:
395:
359:
315:
207:
122:aluminium isopropoxide
113:
36:Organic redox reaction
624:
591:
548:
525:
498:
471:
427:
393:
357:
341:for the oxidation of
321:Woodward modification
313:
205:
173:Dess–Martin oxidation
111:
1065:10.1135/cccc19761056
19:Oppenauer oxidation
1098:10.1021/ja01183a522
864:10.1021/ja01225a001
836:10.1021/ja01594a061
671:Corey–Kim oxidation
409:3-nitrobenzaldehyde
365:Other modifications
358:Woodward modication
80:Oppenauer oxidation
52:oppenauer-oxidation
987:Dewick, P (2001).
627:
594:
566:aldol condensation
551:
528:
501:
474:
430:
402:trimethylaluminium
396:
360:
316:
208:
165:dimethyl sulfoxide
149:aldol condensation
128:. This shifts the
114:
1028:10.1021/jo960361q
1022:(19): 6587–6590.
966:10.1021/cr040679f
930:10.1021/ja063842s
893:10.1021/ol020094c
852:J. Am. Chem. Soc.
830:(13): 3199–3201.
824:J. Am. Chem. Soc.
807:978-7-03-019190-8
636:Alcohol oxidation
536:from 1,4 and 1,5
77:
76:
1190:
1158:
1157:
1137:
1131:
1130:
1108:
1102:
1101:
1075:
1069:
1068:
1059:(4): 1056–1065.
1046:
1040:
1039:
1009:
1003:
1002:
984:
978:
977:
948:
942:
941:
911:
905:
904:
874:
868:
867:
846:
840:
839:
818:
812:
811:
793:
782:
781:
769:
763:
762:
738:
732:
731:
708:
455:. For instance,
274:carboxylic acids
266:chemoselectivity
242:transition state
92:
69:
54:
16:
15:
1198:
1197:
1193:
1192:
1191:
1189:
1188:
1187:
1163:
1162:
1161:
1138:
1134:
1109:
1105:
1081:
1076:
1072:
1047:
1043:
1010:
1006:
999:
985:
981:
949:
945:
924:(39): 12596–7.
912:
908:
887:(16): 2669–72.
880:Organic Letters
875:
871:
847:
843:
819:
815:
808:
794:
785:
770:
766:
739:
735:
709:
705:
701:
666:Swern oxidation
646:Jones oxidation
632:
616:allylic alcohol
558:
437:
367:
323:
291:
286:
278:Jones oxidation
250:
198:
169:Swern oxidation
86:
65:
50:
12:
11:
5:
1196:
1186:
1185:
1183:Name reactions
1180:
1175:
1160:
1159:
1148:(5): 323–325.
1132:
1103:
1079:
1070:
1041:
1004:
997:
979:
960:(7): 2943–89.
943:
906:
869:
841:
813:
806:
783:
764:
753:(5): 178–223.
733:
722:(2): 137–144.
702:
700:
697:
696:
695:
689:
679:
673:
668:
663:
658:
653:
648:
643:
638:
631:
628:
596:
595:
557:
556:Side reactions
554:
553:
552:
530:
529:
503:
502:
476:
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436:
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432:
431:
398:
397:
366:
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361:
322:
319:
318:
317:
290:
287:
285:
282:
249:
246:
210:
209:
197:
194:
82:, named after
75:
74:
71:
70:
63:
56:
55:
48:
44:
43:
39:
38:
33:
32:Reaction type
29:
28:
25:
21:
20:
9:
6:
4:
3:
2:
1195:
1184:
1181:
1179:
1176:
1174:
1171:
1170:
1168:
1155:
1151:
1147:
1143:
1136:
1128:
1124:
1120:
1116:
1115:
1107:
1099:
1095:
1091:
1087:
1086:
1074:
1066:
1062:
1058:
1054:
1053:
1045:
1037:
1033:
1029:
1025:
1021:
1018:
1017:
1016:J. Org. Chem.
1008:
1000:
994:
990:
983:
975:
971:
967:
963:
959:
956:
955:
947:
939:
935:
931:
927:
923:
919:
918:
910:
902:
898:
894:
890:
886:
882:
881:
873:
865:
861:
857:
854:
853:
845:
837:
833:
829:
826:
825:
817:
809:
803:
799:
792:
790:
788:
779:
775:
768:
760:
756:
752:
749:
748:
743:
737:
729:
725:
721:
718:(in German).
717:
716:
707:
703:
693:
690:
687:
683:
682:Ley oxidation
680:
677:
674:
672:
669:
667:
664:
662:
659:
657:
654:
652:
649:
647:
644:
642:
639:
637:
634:
633:
623:
619:
617:
613:
609:
605:
601:
598:Another side
590:
586:
585:
584:
582:
579:
575:
571:
567:
563:
547:
543:
542:
541:
539:
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520:
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518:
516:
512:
508:
497:
493:
492:
491:
489:
485:
481:
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466:
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464:
462:
458:
454:
450:
446:
442:
426:
422:
421:
420:
418:
414:
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407:
403:
392:
388:
387:
386:
384:
380:
376:
372:
356:
352:
351:
350:
348:
344:
340:
336:
332:
328:
312:
308:
307:
306:
304:
300:
296:
284:Modifications
281:
279:
275:
271:
267:
263:
259:
255:
245:
243:
239:
235:
231:
227:
223:
219:
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204:
200:
199:
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187:
183:
179:
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170:
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162:
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142:
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133:
131:
127:
123:
119:
110:
106:
104:
100:
96:
90:
85:
81:
72:
68:
64:
61:
58:
57:
53:
49:
46:
45:
40:
37:
34:
31:
30:
26:
23:
22:
17:
1145:
1141:
1135:
1118:
1112:
1106:
1089:
1083:
1073:
1056:
1052:ChemPlusChem
1050:
1044:
1019:
1014:
1007:
988:
982:
957:
952:
946:
921:
915:
909:
884:
878:
872:
855:
850:
844:
827:
822:
816:
800:. Elsevier.
797:
777:
773:
767:
750:
745:
742:Wilds, A. L.
736:
719:
713:
706:
618:substrates.
606:reaction of
597:
559:
531:
504:
488:pregnenolone
484:Progesterone
477:
438:
399:
368:
339:benzophenone
330:
324:
299:benzoquinone
292:
251:
226:intermediate
211:
134:
115:
79:
78:
67:RXNO:0000047
62:ontology ID
42:Identifiers
24:Named after
1092:(3): 1292.
858:(9): 1425.
747:Org. React.
578:unsaturated
564:-catalyzed
130:equilibrium
87: [
1167:Categories
1121:(5): 323.
1082:Ketone)".
998:0471496405
954:Chem. Rev.
780:: 149–153.
699:References
688:oxidation)
441:analgesics
413:isoborneol
383:terpenoids
260:(PCC) and
248:Advantages
124:in excess
97:secondary
694:oxidation
678:oxidation
612:anhydrous
604:Tischenko
581:aldehydes
574:aldehydes
511:ruthenium
457:codeinone
371:catalysts
270:aldehydes
230:substrate
218:aluminium
214:mechanism
196:Mechanism
186:alkaloids
157:chromates
137:oxidation
95:oxidizing
1036:11667525
974:16836305
938:17002323
901:12153205
630:See also
608:aldehyde
600:reaction
576:or α, ß-
570:aldehyde
534:lactones
515:steroids
480:hormones
449:morphine
447:such as
406:aldehyde
404:and the
347:nitrogen
303:hydrogen
295:steroids
238:carbonyl
222:alkoxide
190:terpenes
182:hormones
178:steroids
153:aldehyde
145:sulfides
99:alcohols
602:is the
507:steroid
461:codeine
453:codeine
443:in the
417:camphor
379:carvone
375:carveol
343:quinine
301:as the
254:benzene
234:hydride
192:, etc.
126:acetone
103:ketones
1034:
995:
972:
936:
899:
804:
167:(e.g.
159:(e.g.
141:amines
692:TEMPO
538:diols
171:) or
163:) or
91:]
1032:PMID
993:ISBN
970:PMID
934:PMID
897:PMID
802:ISBN
686:TPAP
562:base
451:and
337:and
143:and
135:The
1150:doi
1123:doi
1094:doi
1061:doi
1024:doi
962:doi
958:106
926:doi
922:128
889:doi
860:doi
832:doi
755:doi
724:doi
583:.
568:of
415:to
377:to
272:to
151:of
101:to
60:RSC
1169::
1144:.
1117:.
1090:70
1088:.
1080:15
1057:41
1055:.
1030:.
1020:61
968:.
932:.
920:.
895:.
883:.
856:67
828:78
786:^
778:43
776:.
720:56
540:.
490:.
482:.
463:.
419:.
280:.
188:,
184:,
180:,
105:.
89:de
1156:.
1152::
1146:2
1129:.
1125::
1119:2
1100:.
1096::
1067:.
1063::
1038:.
1026::
1001:.
976:.
964::
940:.
928::
903:.
891::
885:4
866:.
862::
838:.
834::
810:.
761:.
757::
751:2
730:.
726::
684:(
Text is available under the Creative Commons Attribution-ShareAlike License. Additional terms may apply.
