114:, both of which result in the inversion of stereochemistry. In path b, the metal is first oxidized without the addition of the halide. The second step occurs with a nucleophilic attack of the α-carbon which again results in the inversion of stereochemistry.
293:
and is followed by nucleophilic abstraction of the α-acyl by MeOH. One of the advantages of this intermolecular nucleophilic abstraction is the production of linear acyl derivatives. The intramolecular attack of these linear acyl derivatives gives rise to
205:
can undergo nucleophilic abstraction where a methyl group is removed. With the addition of a small abstracting agent, the abstracting agent would normally add to the carbene carbon. In this case however, the
106:
to the metal complex. This step results in the oxidized metal center that is needed to weaken the M-C bond. The second step can proceed with either the nucleophilic attack of the halide ion on the
210:
of the abstracting agent that is added causes the abstraction of the methyl group. If the methyl group is replaced with ethyl, the reaction proceeds 70 times slower which is to be expected with a
174:
Nucleophilic abstraction can occur on a ligand of a metal if the conditions are right. For instance the following example shows the nucleophilic abstraction of H from an
433:
159:
journal showed interesting results where one iridium complex undergoes carbonyl abstraction while a very similar iridium complex undergoes hydride extraction.
255:
groups is replaced by a silicon molecule where the bond between the silicon and the hydrogen is coordinating to the ruthenium. In the second step a
382:
358:
311:
284:
246:
223:
191:
164:
150:
93:
75:
50:
is relatively uncommon, there are examples of this type of reaction. In order for this reaction to be favorable, the metal must first be
508:
503:
237:
is a silicon cation with only three bonds and a positive charge. The abstraction of the silylium ion is seen from the
137:
NO on the carbon of the carbonyl group which pushes electrons on the metal. The reaction then proceeds to kick out CO
58:. The oxidation of the metal causes the M-C bond to weaken, which allows for the nucleophilic abstraction to occur.
179:
23:
289:
The following year a similar mechanism was proposed where oxidative addition of an aryl halide followed by
322:
122:
111:
107:
259:
is added for the nucleophilic abstraction of the silylium ion and the hydrogen is left on the metal.
59:
420:
290:
27:
99:
85:
378:
354:
271:
group is seen when MeOH is added to the following palladium complex. The mechanism follows a
34:
which causes part or all of the original ligand to be removed from the metal along with the
295:
202:
81:
80:
It is important to note that the product of this reaction is inverted with respect to the
207:
497:
55:
485:
252:
234:
211:
472:
407:
394:
459:
446:
310:
283:
272:
245:
222:
190:
163:
149:
92:
74:
47:
35:
70:
as M-C cleaving agents in the following example of nucleophilic abstraction.
238:
130:
299:
103:
303:
256:
31:
276:
175:
51:
268:
84:
attached to the metal. There are several possibilities for the
182:
nature of the chromium allows for the reaction to occur as a
88:
of this reaction which are shown in the following schematic.
458:
D. V. Gutsulyak, S. F. Vyboishchikov, and G. I. Nikonov,
183:
129:NO) can be used in the nucleophilic abstraction of
432:C. S. Chin, M. Oh, G. Won, H. Cho, and D. Shin,
251:In the first step of this mechanism one of the
267:One example of nucleophilic abstraction of an
8:
98:In path a, the first step proceeds with the
341:
339:
337:
406:K. Yang, S. G. Bott, and M. G. Richmond,
279:and the reduced palladium complex shown.
275:intermediate which results in the methyl
351:Organometallic Chemistry: Second Edition
133:. There is an nucleophilic attack of Me
369:Xu, Ruren; Pang, Wenqin; Huo, Qisheng (
333:
62:and D.J. Boschetto use the halogens Br
54:because reduced metals are often poor
393:G.M. Whitesides and D. J. Boschetto,
46:While nucleophilic abstraction of an
7:
434:Bull. Korean Chem Soc., 1999, 20, 85
375:Modern Inorganic Synthetic Chemistry
421:J. Coord. Chem. Rev., 1984, 53, 227
157:Bulletin of Korean Chemical Society
26:reaction which can be defined as a
460:J. Am. Chem. Soc., 2010, 132, 5950
14:
395:J. Am. Chem. Soc., 1971, 93, 1529
345:Spessard, Gary; Miessler, Gary (
309:
282:
244:
221:
189:
162:
148:
91:
73:
486:Pure Appl. Chem., 1978, 50, 691
471:J. K. Stille and K. S. Y. Lau,
445:L. M. Toomey and J. D. Atwood,
408:Organometallics, 1994, 13, 3788
16:Type of organometallic reaction
473:Acc. Chem. Res., 1977, 10, 434
447:Organometallics, 1997, 16, 490
1:
419:M. O. Albers and N. Coville,
178:attached to chromium. The
525:
509:Organometallic chemistry
20:Nucleophilic abstraction
323:Addition to pi ligands
291:migratory CO insertion
123:Trimethylamine N-oxide
110:of the alkyl group or
241:complex shown below.
112:reductive elimination
82:stereochemical center
229:Silylium abstraction
180:electron withdrawing
170:Hydrogen abstraction
155:An article from the
118:Carbonyl abstraction
504:Inorganic chemistry
28:nucleophilic attack
263:α-Acyl abstraction
197:Methyl abstraction
100:oxidative addition
383:978-0-444-53599-3
359:978-0-19-533099-1
42:Alkyl abstraction
516:
489:
482:
476:
469:
463:
456:
450:
443:
437:
430:
424:
417:
411:
404:
398:
391:
385:
367:
361:
343:
313:
296:cyclic compounds
286:
248:
225:
193:
166:
152:
95:
77:
22:is a type of an
524:
523:
519:
518:
517:
515:
514:
513:
494:
493:
492:
483:
479:
470:
466:
457:
453:
444:
440:
431:
427:
418:
414:
405:
401:
392:
388:
368:
364:
344:
335:
331:
319:
265:
231:
215:
203:Fischer carbene
199:
172:
144:
140:
136:
128:
120:
69:
65:
60:G.M. Whitesides
44:
17:
12:
11:
5:
522:
520:
512:
511:
506:
496:
495:
491:
490:
477:
464:
451:
438:
425:
412:
399:
386:
377:. pp. 275-278
362:
353:. pp. 285-289
332:
330:
327:
326:
325:
318:
315:
264:
261:
230:
227:
216:2 displacement
213:
198:
195:
171:
168:
142:
138:
134:
126:
119:
116:
67:
63:
56:leaving groups
43:
40:
24:organometallic
15:
13:
10:
9:
6:
4:
3:
2:
521:
510:
507:
505:
502:
501:
499:
487:
481:
478:
474:
468:
465:
461:
455:
452:
448:
442:
439:
435:
429:
426:
422:
416:
413:
409:
403:
400:
396:
390:
387:
384:
380:
376:
372:
366:
363:
360:
356:
352:
348:
342:
340:
338:
334:
328:
324:
321:
320:
316:
314:
312:
307:
305:
301:
297:
292:
287:
285:
280:
278:
274:
270:
262:
260:
258:
254:
249:
247:
242:
240:
236:
228:
226:
224:
219:
217:
209:
204:
196:
194:
192:
187:
185:
181:
177:
169:
167:
165:
160:
158:
153:
151:
146:
132:
124:
117:
115:
113:
109:
105:
101:
96:
94:
89:
87:
83:
78:
76:
71:
61:
57:
53:
49:
41:
39:
37:
33:
29:
25:
21:
484:R. F. Heck,
480:
467:
454:
441:
428:
415:
402:
389:
374:
370:
365:
350:
346:
308:
288:
281:
266:
253:acetonitrile
250:
243:
235:silylium ion
232:
220:
200:
188:
176:arene ligand
173:
161:
156:
154:
147:
121:
97:
90:
79:
72:
45:
19:
18:
273:tetrahedral
218:mechanism.
208:steric bulk
48:alkyl group
36:nucleophile
498:Categories
329:References
186:reaction.
239:ruthenium
86:mechanism
317:See also
300:lactones
298:such as
131:carbonyl
108:α-carbon
52:oxidized
304:lactams
141:and NMe
104:halogen
102:of the
381:
357:
269:α-acyl
257:ketone
184:facile
32:ligand
277:ester
66:and I
30:on a
379:ISBN
371:2011
355:ISBN
347:2010
302:or
125:(Me
500::
373:).
349:).
336:^
306:.
233:A
201:A
145:.
38:.
488:.
475:.
462:.
449:.
436:.
423:.
410:.
397:.
214:N
212:S
143:3
139:2
135:3
127:3
68:2
64:2
Text is available under the Creative Commons Attribution-ShareAlike License. Additional terms may apply.
