276:
131:
213:
60:
755:
Matsubara, Toshiaki; Koga, Nobuaki; Musaev, Djamaladdin G.; Morokuma, Keiji (1998-12-01). "Density
Functional Study on Activation of ortho-CH Bond in Aromatic Ketone by Ru Complex. Role of Unusual Five-Coordinated d6 Metallacycle Intermediate with Agostic Interaction".
890:
Kakiuchi, Fumitoshi; Kochi, Takuya; Mizushima, Eiichiro; Murai, Shinji (2010-12-22). "Room-Temperature
Regioselective CāH/Olefin Coupling of Aromatic Ketones Using an Activated Ruthenium Catalyst with a Carbonyl Ligand and Structural Elucidation of Key Intermediates".
275:
130:
791:
Matsubara, Toshiaki; Koga, Nobuaki; Musaev, Djamaladdin G.; Morokuma, Keiji (2000-06-01). "Density
Functional Study on Highly Ortho-Selective Addition of an Aromatic CH Bond to Olefins Catalyzed by a Ru(H)2(CO)(PR3)3 Complex".
51:
catalyst. The reaction, named after Shinji Murai, was first reported in 1993. While not the first example of C-H activation, the Murai reaction is notable for its high efficiency and scope. Previous examples of such
862:
Buskens, Pascal; Giunta, Daniela; Leitner, Walter (2004-04-20). "Activation and deactivation of a carbene containing non-classical ruthenium hydride complex in catalytic processes involving CāH bond cleavage".
388:
Murai, Shinji; Kakiuchi, Fumitoshi; Sekine, Shinya; Tanaka, Yasuo; Kamatani, Asayuki; Sonoda, Motohiro; Chatani, Naoto (1993-12-09). "Efficient catalytic addition of aromatic carbon-hydrogen bonds to olefins".
201:
A detailed mechanism for the Murai reaction has not been elucidated. Experimental and computational studies give evidence for at least two different mechanisms, depending on the
709:
Helmstedt, Ulrike; Clot, Eric (2012-09-03). "Hydride ligands make the difference: density functional study of the mechanism of the Murai reaction catalyzed by (R=cyclohexyl)".
212:
330:), the complex reductively eliminates the product to give the product agostically bound to the complex. Coordination of another acetophenone molecule regenerates complex
827:
Guari, Yannick; Sabo-Etienne, Sylviane; Chaudret, Bruno (1998-05-01). "Exchange
Couplings between a Hydride and a Stretched Dihydrogen Ligand in Ruthenium Complexes".
168:
470:
Murai, Shinji; Chatani, Naoto; Kakiuchi, Fumitoshi (1997-03-01). "Catalytic addition of C-H bonds to multiple bonds with the aid of ruthenium complexes".
625:
626:"Ruthenium-Catalyzed Addition of Carbon-Hydrogen Bonds in Aromatic Ketones to Olefins. The Effect of Various Substituents at the Aromatic Ring"
548:
Kakiuchi, Fumitoshi; Yamamoto, Yoshimi; Chatani, Naoto; Murai, Shinji (1995-08-01). "Catalytic
Addition of Aromatic CāH Bonds to Acetylenes".
353:
Kakiuchi, Fumitoshi; Kochi, Takuya (2008-10-01). "Transition-Metal-Catalyzed Carbon-Carbon Bond
Formation via Carbon-Hydrogen Bond Cleavage".
115:
methyl blocking group. Unfortunately, with ortho methyl groups both the rate and generality of the reaction are reduced. Substituents at the
127:
group capable of coordinating with the Ru catalyst. Methoxyacetophenones show preferential reaction at the more hindered position.
585:"Ruthenium-catalyzed ortho-CāH bond alkylation of aromatic amides with Ī±,Ī²-unsaturated ketones via bidentate-chelation assistance"
134:
Effect of m-substituents on regioselectivity. Percentages are isolated yields of substitution at the indicated position.
183:
59:
939:
206:
100:
alkylation of aromatic rings with Ī±,Ī²-unsaturated ketones, which typically are unreactive in Murai reactions.
429:
Murai, S.; Kakiuchi, F.; Sekine, S.; Tanaka, Y.; Kamatani, Asayuki; Sonoda, M.; Chatani, Naoto (1994-01-01).
505:
Yang, Jiong (2015-02-04). "Transition metal catalyzed meta-CāH functionalization of aromatic compounds".
119:
position influence regioselectivity. The reaction preferentially adds at the least sterically hindered
398:
302:). As in the Ru proposed mechanism, this agostic interaction leads to the oxidative addition of the
280:
279:
Mechanism proposed for the reaction acetophenone and ethylene as catalyzed by . Spectator ligands (
261:
253:
916:
908:
844:
809:
773:
734:
726:
691:
683:
645:
606:
565:
530:
522:
487:
452:
370:
44:
20:
272:
The complex catalyzes the Murai reaction at room temperature. For , the active complex is .
88:, imines, nitriles, and imidates. Murai reactions have also been reported with disubstituted
900:
872:
836:
801:
765:
718:
675:
637:
596:
557:
514:
479:
442:
406:
362:
221:
28:
294:, acetophenone coordinates to the complex via its carbonyl oxygen and agostically via its
81:
64:
402:
53:
32:
933:
209:
studies and experimental evidence has resulted in the following proposed mechanism:
624:
Sonoda, Motohiro; Kakiuchi, Fumitoshi; Chatani, Naoto; Murai, Shinji (1997-12-01).
257:
666:
Kakiuchi, Fumitoshi; Murai, Shinji (2002-10-01). "Catalytic C-h/olefin coupling".
205:. For catalysts such as which are active as Ru, a combination of computational
314:. Coordination of ethylene and decoordination of the ketone results in complex
876:
483:
318:
which then undergoes migratory insertion of ethylene into the hydride to give
104:
912:
848:
813:
777:
730:
687:
649:
610:
569:
526:
491:
456:
374:
447:
430:
248:
species. The catalytic cycle is proposed to begins with coordination of the
93:
48:
920:
738:
722:
695:
534:
366:
290:
After the active form of the ruthenium catalyst complex is generated from
641:
202:
36:
561:
601:
584:
518:
89:
904:
840:
805:
769:
679:
216:
Proposed mechanism for the reaction of ethene and acetophenone (L = PR
410:
249:
77:
40:
143:
A variety of Ru catalysts catalyze the Murai reaction, including RuH
274:
211:
129:
85:
58:
103:
Early examples of the reaction suffered from side products of
84:, but other functional groups have been reported, including
111:
positions. This problem can be partially solved using an
264:. The C-C bond formation is the rate limiting step.
56:required more forcing conditions and narrow scope.
76:The reaction was initially demonstrated using a
256:of a C-H bond. The resulting five-coordinated
8:
867:. Protagonists in Chemistry: Helmut Werner.
310:, which remains coordinated, giving complex
228:It is proposed that at high temperatures RuH
583:Rouquet, Guy; Chatani, Naoto (2013-04-02).
630:Bulletin of the Chemical Society of Japan
600:
446:
893:Journal of the American Chemical Society
829:Journal of the American Chemical Society
758:Journal of the American Chemical Society
39:between a terminal or strained internal
342:
750:
748:
306:C-H. Reductive elimination releases H
240:converts to an unsaturated Ru(CO)(PPh
7:
661:
659:
424:
422:
420:
348:
346:
322:. Following oxidative addition of H
14:
123:position, except when there is a
431:"Catalytic C-H/olefin coupling"
1:
711:Chemistry: A European Journal
668:Accounts of Chemical Research
16:Reaction in organic chemistry
472:Catalysis Surveys from Asia
956:
435:Pure and Applied Chemistry
877:10.1016/j.ica.2004.01.018
72:Scope and regiochemistry
865:Inorganica Chimica Acta
484:10.1023/A:1019064627386
448:10.1351/pac199466071527
96:directing groups allow
723:10.1002/chem.201200757
367:10.1055/s-2008-1067256
287:
286:) omitted for clarity.
225:
135:
68:
278:
215:
133:
62:
642:10.1246/bcsj.70.3117
260:is stabilized by an
63:Murai reaction; X =
899:(50): 17741ā17750.
764:(48): 12692ā12693.
717:(36): 11449ā11458.
562:10.1246/cl.1995.681
403:1993Natur.366..529M
262:agostic interaction
602:10.1039/c3sc50310k
519:10.1039/c4ob02171a
288:
254:oxidative addition
226:
224:on Ru are omitted.
207:density functional
136:
69:
940:Organic reactions
905:10.1021/ja104918f
841:10.1021/ja971603m
835:(17): 4228ā4229.
806:10.1021/om0001220
800:(12): 2318ā2329.
770:10.1021/ja9816943
680:10.1021/ar960318p
636:(12): 3117ā3128.
550:Chemistry Letters
507:Org. Biomol. Chem
397:(6455): 529ā531.
361:(19): 3013ā3039.
222:spectator ligands
45:aromatic compound
21:organic chemistry
947:
925:
924:
887:
881:
880:
871:(6): 1969ā1974.
859:
853:
852:
824:
818:
817:
788:
782:
781:
752:
743:
742:
706:
700:
699:
663:
654:
653:
621:
615:
614:
604:
589:Chemical Science
580:
574:
573:
545:
539:
538:
513:(7): 1930ā1941.
502:
496:
495:
467:
461:
460:
450:
441:(7): 1527ā1534.
426:
415:
414:
411:10.1038/366529a0
385:
379:
378:
350:
268:Ru(II) catalysts
35:to create a new
29:organic reaction
955:
954:
950:
949:
948:
946:
945:
944:
930:
929:
928:
889:
888:
884:
861:
860:
856:
826:
825:
821:
794:Organometallics
790:
789:
785:
754:
753:
746:
708:
707:
703:
674:(10): 826ā834.
665:
664:
657:
623:
622:
618:
582:
581:
577:
547:
546:
542:
504:
503:
499:
469:
468:
464:
428:
427:
418:
387:
386:
382:
352:
351:
344:
340:
325:
309:
284:
270:
247:
243:
239:
235:
231:
219:
199:
197:Ru(0) catalysts
191:
187:
180:
176:
172:
166:
162:
158:
154:
150:
146:
141:
82:directing group
74:
65:directing group
54:hydroarylations
17:
12:
11:
5:
953:
951:
943:
942:
932:
931:
927:
926:
882:
854:
819:
783:
744:
701:
655:
616:
575:
556:(8): 681ā682.
540:
497:
462:
416:
380:
341:
339:
336:
323:
307:
282:
269:
266:
245:
241:
237:
233:
229:
217:
198:
195:
189:
185:
178:
174:
170:
164:
160:
156:
152:
148:
144:
140:
137:
73:
70:
33:C-H activation
25:Murai reaction
15:
13:
10:
9:
6:
4:
3:
2:
952:
941:
938:
937:
935:
922:
918:
914:
910:
906:
902:
898:
894:
886:
883:
878:
874:
870:
866:
858:
855:
850:
846:
842:
838:
834:
830:
823:
820:
815:
811:
807:
803:
799:
795:
787:
784:
779:
775:
771:
767:
763:
759:
751:
749:
745:
740:
736:
732:
728:
724:
720:
716:
712:
705:
702:
697:
693:
689:
685:
681:
677:
673:
669:
662:
660:
656:
651:
647:
643:
639:
635:
631:
627:
620:
617:
612:
608:
603:
598:
594:
590:
586:
579:
576:
571:
567:
563:
559:
555:
551:
544:
541:
536:
532:
528:
524:
520:
516:
512:
508:
501:
498:
493:
489:
485:
481:
477:
473:
466:
463:
458:
454:
449:
444:
440:
436:
432:
425:
423:
421:
417:
412:
408:
404:
400:
396:
392:
384:
381:
376:
372:
368:
364:
360:
356:
349:
347:
343:
337:
335:
333:
329:
321:
317:
313:
305:
301:
297:
293:
285:
277:
273:
267:
265:
263:
259:
255:
251:
223:
214:
210:
208:
204:
196:
194:
192:
181:
138:
132:
128:
126:
122:
118:
114:
110:
106:
101:
99:
95:
91:
87:
83:
79:
71:
66:
61:
57:
55:
50:
46:
42:
38:
34:
30:
26:
22:
896:
892:
885:
868:
864:
857:
832:
828:
822:
797:
793:
786:
761:
757:
714:
710:
704:
671:
667:
633:
629:
619:
592:
588:
578:
553:
549:
543:
510:
506:
500:
478:(1): 35ā51.
475:
471:
465:
438:
434:
394:
390:
383:
358:
354:
331:
327:
319:
315:
311:
303:
299:
295:
291:
289:
271:
258:metallocycle
252:followed by
227:
200:
142:
124:
120:
116:
112:
108:
102:
97:
75:
24:
18:
595:(5): 2201.
338:References
298:C-H bond (
105:alkylation
31:that uses
913:0002-7863
849:0002-7863
814:0276-7333
778:0002-7863
731:1521-3765
688:0001-4842
650:0009-2673
611:2041-6539
570:0366-7022
527:1477-0539
492:1384-6574
457:1365-3075
375:0039-7881
355:Synthesis
139:Mechanism
94:Bidentate
49:ruthenium
934:Category
921:21114294
739:22847874
696:12379135
535:25522930
232:(CO)(PPh
220:). Some
203:catalyst
147:(CO)(PPh
107:at both
47:using a
37:C-C bond
399:Bibcode
90:alkynes
80:as the
43:and an
919:
911:
847:
812:
776:
737:
729:
694:
686:
648:
609:
568:
533:
525:
490:
455:
391:Nature
373:
250:ketone
182:, and
169:Ru(CO)
86:esters
78:ketone
41:alkene
27:is an
23:, the
304:ortho
296:ortho
155:, RuH
121:ortho
113:ortho
109:ortho
98:ortho
917:PMID
909:ISSN
845:ISSN
810:ISSN
774:ISSN
735:PMID
727:ISSN
692:PMID
684:ISSN
646:ISSN
607:ISSN
566:ISSN
531:PMID
523:ISSN
488:ISSN
453:ISSN
371:ISSN
359:2008
188:(CO)
173:(PPh
159:(PPh
125:meta
117:meta
901:doi
897:132
873:doi
869:357
837:doi
833:120
802:doi
766:doi
762:120
719:doi
676:doi
638:doi
597:doi
558:doi
515:doi
480:doi
443:doi
407:doi
395:366
363:doi
281:PMe
19:In
936::
915:.
907:.
895:.
843:.
831:.
808:.
798:19
796:.
772:.
760:.
747:^
733:.
725:.
715:18
713:.
690:.
682:.
672:35
670:.
658:^
644:.
634:70
632:.
628:.
605:.
591:.
587:.
564:.
554:24
552:.
529:.
521:.
511:13
509:.
486:.
474:.
451:.
439:66
437:.
433:.
419:^
405:.
393:.
369:.
357:.
345:^
334:.
193:.
190:12
184:Ru
167:,
92:.
923:.
903::
879:.
875::
851:.
839::
816:.
804::
780:.
768::
741:.
721::
698:.
678::
652:.
640::
613:.
599::
593:4
572:.
560::
537:.
517::
494:.
482::
476:1
459:.
445::
413:.
409::
401::
377:.
365::
332:2
328:6
326:(
324:2
320:5
316:4
312:3
308:2
300:2
292:1
283:3
246:n
244:)
242:3
238:3
236:)
234:3
230:2
218:3
186:3
179:3
177:)
175:3
171:2
165:4
163:)
161:3
157:2
153:3
151:)
149:3
145:2
67:.
Text is available under the Creative Commons Attribution-ShareAlike License. Additional terms may apply.
