331:
161:
260:
218:
283:
730:. Co-complexes of ortho-dilithiated thiophenol or 2-trimethylsilylthiophenol with lithiated TMEDA molecules: synthesis, crystal structures and theoretical studies (TMEDA = N,N,N′,N′-tetramethylethylenediamine) Alexandra Hildebrand, Peter Lönnecke, Luminita Silaghi-Dumitrescu, Ioan Silaghi-Dumitrescu and Evamarie Hey-Hawkins
88:
613:
Directed ortho
Metalation-Boronation and Suzuki-Miyaura Cross Coupling of Pyridine Derivatives: A One-Pot Protocol to Substituted Azabiaryls Manlio Alessi, Andrew L. Larkin, Kevin A. Ogilvie, Laine A. Green, Sunny Lai, Simon Lopez, and Victor Snieckus
682:. Ortho-Lithiothiophenol Equivalents: Generation, Reactions and Applications in Synthesis of Hindered Thiolate Ligands Eric Block, Venkatachalam Eswarakrishnan, Michael Gernon, Gabriel Ofori-Okai, Chantu Saha, Kaluo Tang, Jon Zubieta
666:
Directed ortho-lithiation of lithium thiophenolate. New methodology for the preparation of ortho-substituted thiophenols and related compounds Garret D. Figuly, Cynthia K. Loop, J. C. Martin
307:
Directed metallation is not limited to lithium intermediates or even to an ortho preference. In one study it is found that the reaction product of N,N-dimethylaniline with a complex of
495:
282:
655:
758:
355:(September 1990). "Directed ortho metalation. Tertiary amide and O-carbamate directors in synthetic strategies for polysubstituted aromatics".
160:
242:
139:
45:
234:
87:
259:
801:
31:
399:
217:
330:
312:
53:
308:
757:
David R. Armstrong, William Clegg, Sophie H. Dale, Eva Hevia, Lorna M. Hogg, Gordon W. Honeyman, Robert E. Mulvey
320:
785:. Selected bond lengths in 2: Zn-C bond 203.5 pm in plane with aryl plane, Na-C bond 269 pm at 76° to aryl plane
714:. 2-Phosphino- and 2-Phosphinyl-benzenethiols: New Ligand Types Eric Block, Gabriel Ofori-Okai and Jon Zubieta
591:
Contra-Friedel–Crafts tert-butylation of substituted aromatic rings via directed metallation and sulfinylation
594:
508:
J. V. Hay And T. M. Harris "Dimethylamino-5-methylphenyl)diphenylcarbinol" Org. Synth. 1973, volume 53, 56.
81:
489:
211:
138:
all the while maintaining the acid-base interaction. An electrophile reacts in the next phase in an
731:
579:
466:"Directed lithiation of simple aromatics and heterocycles for synthesis of substituted derivatives"
464:
El-Hiti, Gamal A.; Smith, Keith; Hegazy, Amany S.; Alshammari, Mohammed B.; Masmali, Ali (2015).
715:
699:
683:
667:
421:
395:
316:
286:
Directed ortho metalation-boronation and Suzuki-Miyaura cross coupling of pyridine derivatives
276:
246:
143:
64:
through the intermediary of an aryllithium compound. The DMG interacts with lithium through a
527:
Nicolas Le Fur, Ljubica
Mojovic, Nelly Plé, Alain Turck, Vincent Reboul, and Patrick Metzner
782:
762:
739:
723:
707:
691:
675:
623:
509:
477:
429:
387:
364:
154:
150:
525:
ortho-Metalation of
Enantiopure Aromatic Sulfoxides and Stereocontrolled Addition to Imines
153:
show preference for both the ortho and para position, this reaction demonstrates increased
698:. Directed lithiation of arenethiols Keith Smith, Charles M. Lindsay, Gareth J. Pritchard
352:
323:
zincated complex as a stable crystalline compound. This complex reacts with electrophilic
272:
57:
643:
552:
382:
Gschwend, Heinz W.; Rodriguez, Herman R. (1979). "Heteroatom-Facilitated
Lithiations".
108:
73:
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207:
173:
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104:
49:
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17:
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in another nucleophilic aromatic substitution through an anionic intermediate.
448:
296:
226:
127:
123:
513:
559:
465:
238:
199:-butyl phenyl sulfoxide. On approach to the lithium intermediate, the bulky
766:
184:
DOM has traditionally been applied to tertiary anilines and benzyl amines.
727:
711:
695:
679:
433:
368:
647:
536:
69:
627:
602:
778:
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324:
30:
This article is about
Organolithium chemistry. For other uses, see
575:
415:
Relative
Reactivities of Organometallic Compounds. XX.* Metalation
204:
200:
77:
562:
followed by DOM reaction initiated again by n-butyllithium with
134:
the ring in the nearest ortho- position forming the aryllithium
755:
Directed meta-Metalation Using Alkali-Metal-Mediated
Zincation
558:
and (S)-tert-butyl tert-butanethiosulfinate to enantiopure an
593:
Jonathan
Clayden, Christopher C. Stimson and Martine Keenan
329:
281:
258:
216:
159:
86:
299:
to prepare compounds that are useful as hindered ligands.
642:
is lithiated, then reacted with triisopropoxyborane to a
225:
In another application DOM is applied in placing a bulky
187:
The method has also been applied to the synthesis of
164:
Scheme 2. Scope of DoM reactions (ref. Snieckus 1990)
494:: CS1 maint: DOI inactive as of September 2024 (
168:This reaction type was reported independently by
566:N-tosylimine. The sulfoxide group is removed by
114:in its specific aggregation state (hence (R-Li)
157:because the ortho position alone is targeted.
149:Ordinary electrophilic substitutions with an
8:
761:Volume 45, Issue 23, Pages 3775 - 3778 2006
263:Scheme 4. DOM application ref. Clayden 2006
99:. An aromatic ring system with a DMG group
142:with a strong preference for the lithium
656:Tetrakis(triphenylphosphine)palladium(0)
271:M has also been applied combined with a
759:Angewandte Chemie International Edition
638:In this sequence the starting material
547:Scheme 3. Reaction scheme: reaction of
344:
221:Scheme 3. DOM application ref. Fur 2006
487:
122:since the hetero atom on the DMG is a
80:group.The compound can be produced by
195:, which involves ortho-lithiation of
95:The general principle is outlined in
52:attach themselves exclusively to the
7:
243:electrophilic aromatic substitution
237:and the subsequent reaction to the
140:electrophilic aromatic substitution
130:. The very basic alkyllithium then
91:Scheme 1. Directed ortho metalation
46:electrophilic aromatic substitution
235:nucleophilic aromatic substitution
25:
327:to N,N-dimethyl-3-iodoaniline:
32:Carbon-hydrogen bond activation
1:
482:10.3998/ark.5550190.p008.744
295:DOM has also been used with
229:group in an ortho position (
146:replacing the lithium atom.
68:. Examples of DMG's are the
392:10.1002/0471264180.or026.01
818:
29:
650:and finally reacted with
334:Directed Meta Metallation
38:Directed ortho metalation
622:; 72(5) pp 1588 - 1594.
535:; 71(7) pp 2609 - 2616;
514:10.15227/orgsyn.053.0056
595:Chemical Communications
233:). The lithiation is a
210:is responsible for the
58:direct metalation group
802:Substitution reactions
767:10.1002/anie.200600720
484:(inactive 2024-09-12).
335:
291:Thiophenol derivatives
287:
264:
222:
165:
92:
44:) is an adaptation of
578:group, ee stands for
333:
285:
262:
220:
163:
90:
722:; 111 pp 2327-2329;
646:, then reacted with
245:. In the final step
212:asymmetric induction
732:Dalton Transactions
728:10.1021/ja00188a071
712:10.1021/ja00184a040
696:10.1021/ja00184a039
680:10.1021/ja00184a038
580:enantiomeric excess
434:10.1021/ja01870a037
369:10.1021/cr00104a001
82:directed lithiation
706:; 111 pp 665-669;
690:; 111 pp 658-665.
428:; 61(1); 109-112.
386:. pp. 1–360.
336:
288:
265:
223:
166:
118:) to intermediate
103:interacts with an
93:
716:J. Am. Chem. Soc.
700:J. Am. Chem. Soc.
684:J. Am. Chem. Soc.
674:; 111 pp 654-658
668:J. Am. Chem. Soc.
628:10.1021/jo0620359
422:J. Am. Chem. Soc.
420:, Robert L. Bebb
384:Organic Reactions
317:di-tert-butylzinc
311:, sodium salt of
277:one-pot synthesis
191:benzyl amines in
27:Chemical reaction
16:(Redirected from
809:
786:
783:room temperature
775:
769:
752:
746:
744:10.1039/B511827A
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357:Chemical Reviews
353:Snieckus, Victor
349:
303:Related reaction
155:regioselectivity
151:activating group
126:and lithium the
21:
18:Ortho-lithiation
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273:Suzuki reaction
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644:boronate ester
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601:, 1393 - 1394
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363:(6): 879–933.
343:
342:
340:
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304:
301:
292:
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214:taking place.
181:
178:
115:
74:tertiary amine
56:position of a
26:
24:
14:
13:
10:
9:
6:
4:
3:
2:
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616:J. Org. Chem.
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607:
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587:
584:
581:
577:
573:
569:
568:hydrogenation
565:
564:electrophilic
561:
557:
556:-butyllithium
555:
550:
544:
541:
538:
534:
530:
529:J. Org. Chem.
526:
521:
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250:-butyllithium
249:
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228:
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209:
206:
203:group on the
202:
198:
194:
190:
185:
179:
177:
176:around 1940.
175:
171:
162:
158:
156:
152:
147:
145:
144:ipso position
141:
137:
133:
129:
125:
121:
113:
112:-butyllithium
111:
106:
102:
98:
89:
85:
83:
79:
76:group and an
75:
71:
67:
63:
59:
55:
51:
50:electrophiles
47:
43:
39:
33:
19:
781:reaction at
773:
754:
750:
735:
719:
703:
687:
671:
662:
640:nicotinamide
634:
619:
609:
598:
590:
586:
572:Raney nickel
553:
543:
532:
524:
520:
504:
490:cite journal
473:
469:
459:
451:
440:
425:
418:Henry Gilman
414:
410:
383:
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356:
347:
306:
294:
268:
266:
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230:
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208:electrophile
196:
192:
186:
183:
174:Georg Wittig
170:Henry Gilman
167:
148:
135:
132:deprotonates
119:
109:
105:alkyllithium
100:
96:
94:
84:of anisole.
61:
41:
37:
36:
738:; 967-974;
652:iodobenzene
549:iodobenzene
297:thiophenols
254:nucleophile
189:enantiopure
66:hetero atom
574:. ts is a
454:, 73, 1197
449:Chem. Ber.
401:0471264180
339:References
252:acts as a
227:tert-butyl
128:Lewis acid
124:Lewis base
560:sulfoxide
476:: 19–48.
445:G. Wittig
239:sulfoxide
72:group, a
48:in which
796:Category
777:Solvent
603:Abstract
537:Abstract
231:scheme 4
193:scheme 3
180:Examples
107:such as
97:scheme 1
648:pinacol
470:Arkivoc
447:et al.
70:methoxy
779:hexane
398:
325:iodine
54:ortho-
576:tosyl
570:with
551:with
319:is a
309:TMEDA
275:in a
205:imine
201:tosyl
78:amide
736:2006
720:1989
704:1989
688:1989
672:1989
654:and
620:2007
599:2006
533:2006
496:link
474:2015
452:1940
426:1939
396:ISBN
321:meta
315:and
248:tert
197:tert
172:and
763:doi
740:doi
724:doi
708:doi
692:doi
676:doi
624:doi
510:doi
478:doi
430:doi
388:doi
365:doi
313:TMP
241:an
62:DMG
60:or
42:DoM
798::
734:;
718:;
702:;
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670:;
618:;
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488:{{
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554:n
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390::
371:.
367::
269:o
267:D
136:3
120:2
116:n
110:n
101:1
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