624:
613:
675:
570:
699:
546:
429:
395:
503:
469:
499:. The gain of aromatic stabilization energy when the benzene is formed is the driving force of the reaction. Pd can be used as a catalyst and a temperature of 100 °C is employed. More exotic transfer hydrogenations have been reported, including this intramolecular one:
452:
Prior to the development of catalytic hydrogenation, many methods were developed for the hydrogenation of unsaturated substrates. Many of these methods are only of historical and pedagogical interest. One prominent transfer hydrogenation agent is
1197:
Rueping; Antonchick, A.; Theissmann, T. (2006). "A highly enantioselective BrĂžnsted acid catalyzed cascade reaction: organocatalytic transfer hydrogenation of quinolines and their application in the synthesis of alkaloids".
331:
432:
Complementing traditional diphosphine-based Noyori catalysts are arene-Ru catalysts, which operate similarly. The stoichiometric asymmetric reduction of ketones has long been known, e.g., using chiral borones.
914:
Kitamura, M.; Ohkuma, T.; Inoue, S.; Sayo, N.; Kumobayashi, H.; Akutagawa, S.; Ohta, T.; Takaya, H.; Noyori, R. (1988), "Homogeneous
Asymmetric Hydrogenation of functionalized ketones",
865:
Shimizu, H., Nagasaki, I., Matsumura, K., Sayo, N., and Saito, T. "Developments in
Asymmetric Hydrogenation from an Industrial Perspective" Acc. Chem. Res. 2007, vol. 40, pp. 1385-1393.
623:
942:
Noyori, R.; Ohkuma, T. (2001), "Asymmetric
Catalysis by Architectural and Functional Molecular Engineering: Practical Chemo- and Stereoselective Hydrogenation of Ketones",
612:
856:
T. Ikariya, K. Murata, R. Noyori "Bifunctional
Transition Metal-Based Molecular Catalysts for Asymmetric Syntheses" Org. Biomol. Chem., 2006, volume 4, 393-406.
674:
1044:
Linden, M. V. D.; Roeters, T.; Harting, R.; Stokkingreef, E.; Gelpke, A. S.; Kemperman, G. (2008). "Debottlenecking the
Synthesis Route of Asenapine".
698:
569:
216:
126:
respectively. Often, the donor molecules also function as solvents for the reaction. A large scale application of transfer hydrogenation is
545:
882:
Mashima, K.; Kusano, K.-h.; Sato, N.; Matsumura, Y.-i.; Nozaki, K.; Kumobayashi, H.; Sayo, N.; Hori, Y.; Ishizaki, T. (1994), "Cationic
886:-Ru(II) Halide Complexes: Highly Efficient Catalysts for Stereoselective Asymmetric Hydrogenation of α- and ÎČ-Functionalized Ketones",
726:
388:
822:
Muñiz, Kilian (2005). "Bifunctional Metal-Ligand
Catalysis: Hydrogenations and New Reactions within the Metal-(Di)amine Scaffold13".
595:, then proton transfer is followed by hydrolysis of the iminium bond regenerating the catalyst. By adopting a chiral imidazolidinone
916:
944:
425:)(diamine). These catalysts preferentially reduce ketones and aldehydes, leaving olefins and many other substituents unaffected.
958:
980:
Dub, Pavel A.; Gordon, John C. (2018). "The role of the metal-bound NâH functionality in Noyori-type molecular catalysts".
54:
163:
809:
1248:
888:
576:
1073:"A metal-free transfer hydrogenation: organocatalytic conjugate reduction of alpha,beta-unsaturated aldehydes"
514:
as the proton donors, and alkali metals as electron donors. Of continuing value is the sodium metal-mediated
1243:
1148:
527:
413:
Even though the BINAP-Ru dihalide catalyst could reduce functionalized ketones, the hydrogenation of simple
1238:
398:
Transfer hydrogenation catalyzed by transition metal complexes proceeds by an "outer sphere mechanism."
376:
of the two chiral carbon centers. This work was recognized with the 2001 Nobel Prize in
Chemistry to
391:; however their activities are relatively low by comparison with the transition metal-based systems.
87:. Transfer hydrogenation usually occurs at mild temperature and pressure conditions using organic or
596:
88:
1112:
Ouellet; Tuttle, J.; MacMillan, D. (2005). "Enantioselective organocatalytic hydride reduction".
443:
167:
804:
Speight, J. G. "The
Chemistry and Technology of Coal" Marcel Dekker; New York, 1983; p. 226 ff.
1253:
690:
384:
373:
175:
58:
92:
523:
502:
468:
383:
Another family of hydrogen-transfer agents are those based on aluminium alkoxides, such as
96:
561:
transfer hydrogenation has been described by the group of List in 2004 in a system with a
8:
731:
604:
187:
65:
1179:
997:
751:
600:
203:
1215:
1171:
1129:
1094:
1001:
963:
839:
805:
787:
631:
143:
127:
108:
50:
40:
36:
28:
1183:
1207:
1163:
1121:
1084:
1053:
1026:
1017:
989:
953:
925:
897:
866:
831:
779:
686:
681:
With another organocatalyst altogether, hydrogenation can also be accomplished for
736:
588:
558:
515:
783:
377:
770:
Wang, Dong; Astruc, Didier (2015). "The Golden Age of
Transfer Hydrogenation".
746:
714:
562:
488:
417:
remained unsolved. This challenge was solved with precatalysts of the type RuCl
993:
146:, a useful family of hydrogen-transfer catalysts have been developed based on
1232:
791:
741:
84:
1219:
1211:
1175:
1133:
1098:
1089:
1072:
967:
843:
835:
207:
1015:
M. M. Midland (1989). "Asymmetric reductions with organoborane reagents".
202:
upon donation of hydrogen. Transfer hydrogenations can proceed with high
706:
592:
484:
422:
349:
195:
104:
100:
1030:
929:
901:
913:
643:
326:{\displaystyle {\ce {RR'C=O{}+Me2CHOH->RR'C^{\star }H-OH{}+Me2C=O}}}
123:
1167:
1125:
1057:
870:
959:
10.1002/1521-3773(20010105)40:1<40::aid-anie40>3.0.co;2-5
539:
531:
477:
171:
159:
147:
20:
710:
639:
635:
580:
535:
131:
32:
461:, also called diazene. This becomes oxidized to the very stable N
194:, respectively. The hydrogen-donor (transfer agent) is typically
662:
496:
454:
447:
414:
403:
199:
155:
151:
119:
1043:
658:
650:
492:
428:
179:
61:
883:
682:
669:) and of the Hantzsch ester (add more bulky t-butyl groups):
666:
654:
511:
407:
394:
191:
183:
162:
ligands. A representative catalyst precursor is derived from
73:
69:
1196:
1070:
591:
for this reaction the amine and the aldehyde first form an
584:
881:
1149:"Organocatalytic transfer hydrogenation of cyclic enones"
553:
308:
255:
583:
form and resembles the biochemically relevant coenzyme
483:
Two hydrocarbons that can serve as hydrogen donors are
1146:
1111:
709:. Traditional metal-based catalysts, hydrogenation of
219:
941:
538:
is used in alkene reductions, e.g. the synthesis of
549:
Magnesium methanol reduction in asenapine synthesis
406:was demonstrated with ruthenium-based complexes of
1200:Angewandte Chemie International Edition in English
1077:Angewandte Chemie International Edition in English
325:
76:. It avoids the need for high-pressure molecular
1230:
1071:Yang; Hechavarria Fonseca, M.; List, B. (2004).
575:In this particular reaction the substrate is an
16:Addition of non-molecular hydrogen to a compound
763:
1014:
649:Extending the scope of this reaction towards
49:. It is applied in laboratory and industrial
657:requires fine tuning of the catalyst (add a
340:is a chiral product. A typical catalyst is
1147:Tuttle; Ouellet, S.; MacMillan, D. (2006).
137:
99:. It uses hydrogen donor compounds such as
1046:Organic Process Research & Development
907:
769:
402:The catalytic asymmetric hydrogenation of
1088:
979:
957:
935:
1156:Journal of the American Chemical Society
1114:Journal of the American Chemical Society
917:Journal of the American Chemical Society
875:
565:as hydride donor and an amine catalyst:
427:
393:
945:Angewandte Chemie International Edition
824:Angewandte Chemie International Edition
1231:
579:. The proton donor is oxidized to the
554:Organocatalytic transfer hydrogenation
480:or certain other organic precursors.
973:
821:
510:Many reactions exist with alcohol or
526:). Less important presently is the
437:
705:The reaction proceeds via a chiral
13:
1008:
727:MeerweinâPonndorfâVerley reduction
544:
501:
476:The diimide can be generated from
467:
164:(cymene)ruthenium dichloride dimer
14:
1265:
577:α,ÎČ-unsaturated carbonyl compound
889:The Journal of Organic Chemistry
697:
673:
622:
611:
568:
1190:
1140:
1105:
1064:
1037:
642:in this reaction yield the (S)-
530:of esters. The combination of
130:using "donor solvents" such as
859:
850:
815:
798:
261:
206:when the starting material is
1:
757:
91:catalysts, many of which are
174:are mainly employed for the
7:
784:10.1021/acs.chemrev.5b00203
720:
10:
1270:
441:
111:, dehydrogenating them to
31:involving the addition of
994:10.1038/s41570-018-0049-z
717:substrates tend to fail.
528:BouveaultâBlanc reduction
39:from a source other than
982:Nature Reviews Chemistry
597:MacMillan organocatalyst
495:is formed, along with a
138:Organometallic catalysts
1249:Organic redox reactions
444:reductions with diimide
348:, where Ts refers to a
168:diphenylethylenediamine
1212:10.1002/anie.200600191
1090:10.1002/anie.200461816
836:10.1002/anie.200501787
691:chiral phosphoric acid
661:group and replace the
550:
507:
506:Transfer hydrogenation
473:
472:Transfer hydrogenation
434:
399:
385:aluminium isopropoxide
374:absolute configuration
327:
154:complexes, often with
57:organic compounds and
25:transfer hydrogenation
548:
524:aromatic hydrocarbons
505:
471:
431:
397:
328:
95:, allowing efficient
83:used in conventional
1244:Industrial processes
491:. In this case, an
217:
204:enantioselectivities
198:, which converts to
97:asymmetric synthesis
1162:(39): 12662â12663.
1031:10.1021/cr00097a010
930:10.1021/ja00210a070
902:10.1021/jo00090a026
732:Oppenauer oxidation
310:
257:
1239:Chemical processes
752:Borrowing hydrogen
689:is catalyzed by a
601:enantioselectivity
551:
522:(another name for
508:
474:
435:
400:
323:
298:
245:
166:and the tosylated
1206:(22): 3683â3686.
1168:10.1021/ja0653066
1126:10.1021/ja043834g
1083:(48): 6660â6662.
1058:10.1021/op700240c
896:(11): 3064â3076,
871:10.1021/ar700101x
830:(41): 6622â6627.
778:(13): 6621â6686.
632:stereoconvergence
438:Metal-free routes
321:
313:
301:
292:
284:
275:
267:
260:
248:
239:
231:
224:
144:organic synthesis
128:coal liquefaction
109:dihydroanthracene
51:organic synthesis
29:chemical reaction
1261:
1224:
1223:
1194:
1188:
1187:
1153:
1144:
1138:
1137:
1109:
1103:
1102:
1092:
1068:
1062:
1061:
1041:
1035:
1034:
1025:(7): 1553â1561.
1018:Chemical Reviews
1012:
1006:
1005:
977:
971:
970:
961:
939:
933:
932:
911:
905:
904:
879:
873:
863:
857:
854:
848:
847:
819:
813:
802:
796:
795:
767:
701:
687:cascade reaction
677:
626:
615:
572:
367:
347:
339:
332:
330:
329:
324:
322:
319:
318:
311:
309:
306:
299:
294:
290:
289:
282:
281:
280:
273:
271:
265:
258:
256:
253:
246:
241:
237:
236:
229:
228:
222:
117:
82:
48:
1269:
1268:
1264:
1263:
1262:
1260:
1259:
1258:
1229:
1228:
1227:
1195:
1191:
1151:
1145:
1141:
1110:
1106:
1069:
1065:
1042:
1038:
1013:
1009:
988:(12): 396â408.
978:
974:
940:
936:
912:
908:
880:
876:
864:
860:
855:
851:
820:
816:
803:
799:
768:
764:
760:
737:Dehydrogenation
723:
589:catalytic cycle
559:Organocatalytic
556:
516:Birch reduction
464:
460:
450:
440:
420:
365:
361:
357:
353:
341:
337:
314:
307:
302:
293:
285:
276:
272:
264:
254:
249:
240:
232:
221:
220:
218:
215:
214:
142:In the area of
140:
116:
112:
81:
77:
47:
43:
17:
12:
11:
5:
1267:
1257:
1256:
1251:
1246:
1241:
1226:
1225:
1189:
1139:
1104:
1063:
1052:(2): 196â201.
1036:
1007:
972:
934:
924:(2): 629â631,
906:
874:
858:
849:
814:
797:
761:
759:
756:
755:
754:
749:
747:Hydrogenolysis
744:
739:
734:
729:
722:
719:
715:heteroaromatic
703:
702:
679:
678:
628:
627:
617:
616:
607:was obtained:
563:Hantzsch ester
555:
552:
489:cyclohexadiene
462:
458:
439:
436:
418:
372:refers to the
363:
359:
355:
346:-HNCHPhCHPhNTs
334:
333:
317:
305:
297:
288:
279:
270:
263:
252:
244:
235:
227:
139:
136:
114:
89:organometallic
79:
45:
15:
9:
6:
4:
3:
2:
1266:
1255:
1254:Hydrogenation
1252:
1250:
1247:
1245:
1242:
1240:
1237:
1236:
1234:
1221:
1217:
1213:
1209:
1205:
1201:
1193:
1185:
1181:
1177:
1173:
1169:
1165:
1161:
1157:
1150:
1143:
1135:
1131:
1127:
1123:
1119:
1115:
1108:
1100:
1096:
1091:
1086:
1082:
1078:
1074:
1067:
1059:
1055:
1051:
1047:
1040:
1032:
1028:
1024:
1020:
1019:
1011:
1003:
999:
995:
991:
987:
983:
976:
969:
965:
960:
955:
951:
947:
946:
938:
931:
927:
923:
919:
918:
910:
903:
899:
895:
891:
890:
885:
878:
872:
868:
862:
853:
845:
841:
837:
833:
829:
825:
818:
811:
810:0-8247-1915-8
807:
801:
793:
789:
785:
781:
777:
773:
766:
762:
753:
750:
748:
745:
743:
742:Hydrogenation
740:
738:
735:
733:
730:
728:
725:
724:
718:
716:
712:
708:
700:
696:
695:
694:
692:
688:
684:
676:
672:
671:
670:
668:
664:
660:
656:
652:
647:
645:
641:
637:
633:
630:In a case of
625:
621:
620:
619:
614:
610:
609:
608:
606:
602:
598:
594:
590:
586:
582:
578:
573:
571:
566:
564:
560:
547:
543:
541:
537:
533:
529:
525:
521:
517:
513:
504:
500:
498:
494:
490:
486:
481:
479:
470:
466:
456:
449:
445:
430:
426:
424:
416:
411:
409:
405:
396:
392:
390:
389:MPV reduction
386:
381:
379:
375:
371:
351:
345:
315:
303:
295:
286:
277:
268:
250:
242:
233:
225:
213:
212:
211:
209:
205:
201:
197:
193:
189:
185:
181:
177:
173:
169:
165:
161:
157:
153:
149:
145:
135:
133:
129:
125:
121:
110:
106:
102:
98:
94:
90:
86:
85:hydrogenation
75:
71:
67:
63:
60:
56:
52:
42:
38:
34:
30:
26:
22:
1203:
1199:
1192:
1159:
1155:
1142:
1120:(1): 32â33.
1117:
1113:
1107:
1080:
1076:
1066:
1049:
1045:
1039:
1022:
1016:
1010:
985:
981:
975:
952:(1): 40â73,
949:
943:
937:
921:
915:
909:
893:
887:
877:
861:
852:
827:
823:
817:
800:
775:
771:
765:
704:
680:
648:
629:
618:
574:
567:
557:
519:
509:
482:
475:
451:
412:
401:
382:
378:RyĆji Noyori
369:
343:
335:
141:
24:
18:
707:iminium ion
665:group by a
634:, both the
593:iminium ion
485:cyclohexene
423:diphosphane
350:tosyl group
196:isopropanol
105:isopropanol
101:formic acid
1233:Categories
758:References
653:or rather
644:enantiomer
442:See also:
124:anthracene
1002:106394152
792:0009-2665
772:Chem. Rev
587:. In the
540:asenapine
532:magnesium
478:hydrazine
338:RR'C*HâOH
287:−
278:⋆
262:⟶
208:prochiral
176:reduction
172:catalysts
160:phosphine
148:ruthenium
41:molecular
21:chemistry
1220:16639754
1184:12456921
1176:17002356
1134:15631434
1099:15540245
968:11169691
844:16187395
721:See also
711:aromatic
640:Z-isomer
638:and the
636:E-isomer
581:pyridine
536:methanol
342:(cymene)
269:′
226:′
188:alcohols
170:. These
132:tetralin
66:alcohols
55:saturate
37:compound
33:hydrogen
663:t-butyl
651:ketones
603:of 81%
497:benzene
457:or (NH)
455:diimide
448:quinone
415:ketones
404:ketones
387:in the
200:acetone
180:ketones
156:diamine
152:rhodium
120:acetone
62:ketones
1218:
1182:
1174:
1132:
1097:
1000:
966:
842:
808:
790:
685:. One
683:imines
659:benzyl
655:enones
520:arenes
512:amines
493:alkane
368:) and
336:where
192:amines
184:imines
93:chiral
74:amines
70:imines
68:, and
59:reduce
1180:S2CID
1152:(PDF)
998:S2CID
884:BINAP
667:furan
408:BINAP
122:, or
35:to a
27:is a
1216:PMID
1172:PMID
1130:PMID
1095:PMID
964:PMID
840:PMID
806:ISBN
788:ISSN
585:NADH
534:and
446:and
259:CHOH
190:and
182:and
158:and
150:and
1208:doi
1164:doi
1160:128
1122:doi
1118:127
1085:doi
1054:doi
1027:doi
990:doi
954:doi
926:doi
922:110
898:doi
867:doi
832:doi
780:doi
776:115
713:or
599:an
518:of
487:or
370:R,R
344:R,R
186:to
178:of
107:or
103:,
72:to
64:to
53:to
19:In
1235::
1214:.
1204:45
1202:.
1178:.
1170:.
1158:.
1154:.
1128:.
1116:.
1093:.
1081:43
1079:.
1075:.
1050:12
1048:.
1023:89
1021:.
996:.
984:.
962:,
950:40
948:,
920:,
894:59
892:,
838:.
828:44
826:.
786:.
774:.
693::
646:.
605:ee
542::
465::
410:.
380:.
366:Me
354:SO
300:Me
291:OH
266:RR
247:Me
223:RR
210::
134:.
118:,
113:CO
23:,
1222:.
1210::
1186:.
1166::
1136:.
1124::
1101:.
1087::
1060:.
1056::
1033:.
1029::
1004:.
992::
986:2
956::
928::
900::
869::
846:.
834::
812:.
794:.
782::
463:2
459:2
421:(
419:2
364:4
362:H
360:6
358:C
356:2
352:(
320:O
316:=
312:C
304:2
296:+
283:H
274:C
251:2
243:+
238:O
234:=
230:C
115:2
80:2
78:H
46:2
44:H
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