221:
195:
335:
456:
475:
422:
42:
316:
70:
367:
The
Mukaiyama aldol reaction does not follow the Zimmerman-Traxler model. Carreira has described particularly useful asymmetric methodology with silyl ketene acetals, noteworthy for its high levels of enantioselectivity and wide substrate scope. The method works on
394:
Mukaiyama aldol process can also be rendered catalytic and asymmetric. The example shown below works efficiently for aromatic (but not aliphatic) aldehydes and the mechanism is believed to involve a chiral, metal-bound dienolate.
788:
Mukaiyama, Teruaki; Shiina, Isamu; Iwadare, Hayato; Saitoh, Masahiro; Nishimura, Toshihiro; Ohkawa, Naoto; Sakoh, Hiroki; Nishimura, Koji; Tani, Yu-ichirou; Hasegawa, Masatoshi; Yamada, Koji; Saitoh, Katsuyuki (4 January 1999).
671:
Pagenkopf B.L.; Kruger J.; Stojanovic A.; Carreira E.M. (1998). "Mechanistic insights into Cu-catalyzed asymmetric aldol reactions: Chemical and spectroscopic evidence for a metalloenolate intermediate".
346:
is used. First, the Lewis acid activates the aldehyde component followed by carbon-carbon bond formation between the enol silane and the activated aldehyde. With the loss of a chlorosilane the compound
642:
Kruger J.; Carreira E.M. (1998). "Apparent catalytic generation of chiral metal enolates: Enantioselective dienolate additions to aldehydes mediated by Tol-BINAP center Cu(II) fluoride complexes".
748:
DIRECTED ALDOL CONDENSATIONS: β-PHENYLCINNAMALDEHYDE Organic
Syntheses, Coll. Vol. 6, p. 901 (1988); Vol. 50, p. 66 (1970). G. Wittig, A. Hesse, Allan Y. Teranishi and Herbert O. House
761:
House, Herbert O.; Crumrine, David S.; Teranishi, Allan Y.; Olmstead, Hugh D. (May 1973). "Chemistry of carbanions. XXIII. Use of metal complexes to control the aldol condensation".
220:
482:
Utilization of chiral Lewis acid complexes and Lewis bases in asymmetric catalytic processes is the fastest-growing area in the usage of the
Mukaiyama aldol reaction.
194:
644:
615:
685:
586:
455:
334:
807:
790:
474:
399:
384:
421:
429:
Ketone reactions of this type require higher reaction temperatures. For this work
Mukaiyama was inspired by earlier work done by
521:
369:
837:
308:) was used in stoichiometric amounts but truly catalytic systems exist as well. The reaction is also optimized for
376:
for catalytic, asymmetric processes. This may be due to poor electronic and steric differentiation between their
183:) compounds. In this reaction, compounds with various organic groups can be used (see educts). A basic version (
41:
842:
69:
298:
573:
Strategic applications of named reactions in organic synthesis : background and detailed mechanisms
441:
499:
Mukaiyama, T.; Kobayashi, S. (1994). "Tin(II) Enolates in the Aldol, Michael, and
Related Reactions".
437:. Competing work with lithium enolate aldol reactions was published also in 1973 by Herbert O. House.
309:
578:
445:
294:
147:
in 1973. His choice of reactants allows for a crossed aldol reaction between an aldehyde and a
706:
689:
582:
540:
517:
449:
176:
160:
156:
144:
93:
217:
silanes are used in this reaction a mixture of four products occurs, yielding two racemates.
214:
802:
770:
731:
681:
653:
624:
570:
548:
509:
279:
188:
109:
101:
74:
17:
243:-diastereomer is built depends largely on reaction conditions, substrates and Lewis acids.
225:
206:
603:
571:
749:
315:
105:
735:
831:
468:
464:
283:
247:
710:
430:
411:
373:
263:
236:
199:
722:
Wittig, G.; Suchanek, P. (January 1966). "Ăber gezielte aldokondensationenâII".
686:
10.1002/(SICI)1521-3773(19981204)37:22<3124::AID-ANIE3124>3.0.CO;2-1
513:
501:
377:
391:
210:
172:
808:
10.1002/(SICI)1521-3765(19990104)5:1<121::AID-CHEM121>3.0.CO;2-O
287:
693:
608:-silyl enolates â a chira; tridentate chelate as a ligand for titanium(IV)"
604:"Catalytic, enantioselective aldol additions with methyl and ethyl acetate
398:
383:
552:
128:
46:
774:
628:
282:
it produces a diastereomeric mixture of threo (63%) and erythro (19%) β-
415:
136:
56:
657:
27:
Organic reaction between a silyl enol ether and an aldehyde or formate
159:
of the aldehyde. For this reason the reaction is used extensively in
148:
821:
TBS = t-butyldimethylsilyl, Bn = benzyl, PMB = p-methoxybenzyl ether
434:
291:
246:
The archetypical reaction is that of the silyl enol ether of
473:
454:
420:
397:
382:
333:
314:
219:
193:
410:
A typical reaction involving two ketones is that between
750:
http://www.orgsynth.org/orgsyn/prep.asp?prep=cv6p0901
709:, Coll. Vol. 8, p. 323 (1993); Vol. 65, p. 6 (1987).
539:Teruaki Mukaiyama, Koichi Narasaka and Kazuo Banno
433:in 1966 on crossed aldol reactions with lithiated
711:http://www.orgsynth.org/orgsyn/pdfs/CV8P0323.pdf
602:Carreira E.M.; Singer R.A.; Lee W.S. (1994).
351:is built. The desired product, a racemate of
8:
327:Below, the reaction mechanism is shown with
224:Overview of reaction with consideration of
372:aliphatic aldehydes, which are often poor
31:
806:
763:Journal of the American Chemical Society
645:Journal of the American Chemical Society
616:Journal of the American Chemical Society
342:In the cited example the Lewis acid TiCl
304:
297:. In its original scope the Lewis acid (
273:
269:
257:
253:
123:
119:
115:
791:"Asymmetric Total Synthesis of Taxol\R"
564:
562:
560:
491:
444:(1999) two aldol additions, one with a
440:Mukaiyama employed in his rendition of
569:KĂźrti, LĂĄszlĂł; CzakĂł, Barbara (2005).
7:
577:. Elsevier Academic Press. pp.
425:Mukaiyama aldol between two ketones
155:), or a different aldehyde without
459:Mukaiyama aldol in taxol synthesis
359:, is obtained by aqueous work-up.
171:The Mukaiyama aldol addition is a
143:). The reaction was discovered by
25:
478:Mukaiyama asymmetric aldol taxol
338:Mukaiyama Aldol-MechanismusV7 en
68:
40:
463:and a second one with an amine
795:Chemistry â A European Journal
1:
736:10.1016/S0040-4020(01)82193-1
187:= H) without the presence of
179:of enol silanes to carbonyl (
18:Mukaiyama aldol condensation
547:), No.9 pp. 1011â1014
514:10.1002/0471264180.or046.01
198:Simplified overview with a
859:
86:= Alkyl, Aryl, H, OR, SR)
98:Mukaiyama aldol addition
537:New aldol type reaction
167:General reaction scheme
479:
460:
426:
402:
387:
339:
319:
299:titanium tetrachloride
228:
202:
477:
458:
442:taxol total synthesis
424:
401:
386:
337:
318:
286:as well as 6% of the
223:
197:
674:Angew. Chem. Int. Ed
553:10.1246/cl.1973.1011
310:asymmetric synthesis
295:condensation product
775:10.1021/ja00791a039
629:10.1021/ja00098a065
446:ketene silyl acetal
838:Addition reactions
480:
461:
427:
403:
388:
340:
320:
229:
203:
81:= Alkyl, Aryl, H;
769:(10): 3310â3324.
707:Organic Syntheses
658:10.1021/ja973331t
588:978-0-12-429785-2
541:Chemistry Letters
450:magnesium bromide
161:organic synthesis
157:self-condensation
145:Teruaki Mukaiyama
94:organic chemistry
90:
89:
16:(Redirected from
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414:as the enol and
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280:room temperature
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191:is shown below.
189:chiral catalysts
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110:silyl enol ether
102:organic reaction
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75:silyl enol ether
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363:Stereoselection
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328:
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226:stereochemistry
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83:
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60:
54:
53:= Alkyl, Aryl)
50:
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28:
23:
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15:
12:
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5:
856:
854:
846:
845:
843:Name reactions
840:
830:
829:
824:
823:
814:
801:(1): 121â161.
780:
753:
741:
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699:
680:(22): 3124â6.
663:
634:
623:(19): 8837â8.
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489:
487:
484:
407:
404:
390:The analogous
364:
361:
343:
324:
321:
168:
165:
106:aldol reaction
104:and a type of
88:
87:
65:
64:
37:
36:
26:
24:
14:
13:
10:
9:
6:
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511:
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469:triflate salt
466:
465:chiral ligand
457:
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438:
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374:electrophiles
371:
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296:
293:
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284:hydroxyketone
281:
265:
249:
248:cyclohexanone
244:
242:
238:
234:
227:
222:
218:
216:
213:is built. If
212:
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99:
95:
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43:
39:
38:
34:
33:
30:
19:
817:
798:
794:
783:
766:
762:
756:
744:
727:
723:
717:
702:
677:
673:
666:
652:(4): 837â8.
649:
643:
637:
620:
614:
605:
597:
572:
544:
536:
532:
505:
500:
494:
481:
462:
439:
431:Georg Wittig
428:
412:acetophenone
409:
389:
378:enantiofaces
366:
356:
352:
348:
341:
326:
264:benzaldehyde
245:
240:
237:diastereomer
232:
231:Whether the
230:
215:Z- or E-enol
204:
200:stereocenter
170:
118:C=CRâOâSi(CH
97:
91:
29:
730:: 347â358.
724:Tetrahedron
502:Org. React.
448:and excess
211:enantiomers
207:racemic mix
832:Categories
523:0471264180
486:References
471:catalyst:
392:vinylogous
370:unbranched
175:-mediated
173:Lewis acid
108:between a
323:Mechanism
288:exocyclic
127:) and an
694:29711324
177:addition
141:RâOâCH=O
129:aldehyde
47:aldehyde
543:Vol.2 (
416:acetone
262:, with
239:or the
153:>C=O
137:formate
57:formate
35:educts
692:
585:
581:â299.
520:
467:and a
435:imines
149:ketone
133:RâCH=O
100:is an
96:, the
63:= OR)
611:(PDF)
508:: 1.
406:Scope
331:= H:
292:enone
278:. At
135:) or
690:PMID
583:ISBN
545:1973
518:ISBN
355:and
303:TiCl
233:anti
803:doi
771:doi
732:doi
682:doi
654:doi
650:120
625:doi
621:116
579:298
549:doi
510:doi
276:CHO
252:(CH
241:syn
209:of
181:C=O
92:In
55:or
834::
797:.
793:.
767:95
765:.
728:22
726:.
688:.
678:37
676:.
648:.
619:.
613:.
559:^
516:.
506:46
452::
418::
380:.
312:.
301:,
290:,
266:,
260:CO
250:,
205:A
163:.
811:.
805::
799:5
777:.
773::
738:.
734::
696:.
684::
660:.
656::
631:.
627::
606:O
591:.
551::
526:.
512::
357:3
353:2
349:1
344:4
329:R
305:4
274:5
272:H
270:6
268:C
258:5
256:)
254:2
235:-
185:R
151:(
139:(
131:(
124:3
122:)
120:3
116:2
114:R
112:(
84:R
79:R
77:(
61:R
59:(
51:R
49:(
20:)
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