300:
338:
132:
395:
321:
phenylaziridinylhydrazones as arenesulfonylhydrazone equivalents with a catalytic amount of lithium amides. The required phenylaziridinylhydrazone was prepared from the condensation of undecan-6-one with 1-amino-2-phenylaziridine. Treatment of the phenylaziridinylhydrazone with 0.3 equivalents of LDA in ether resulted in the alkene shown below with a
253:
263:
320:
Traditional
Shapiro reactions require stoichiometric (sometimes excess) amounts of base to generate the alkenyllithium reagents. To combat this problem, Yamamoto and coworkers developed an efficient stereoselective and regioselective route to alkenes using a combination of ketone
366:
337:
275:
The position of the alkene in the product is controlled by the site of deprotonation by the organolithium base. In general, the kinetically favored, less substituted site of differentially substituted tosylhydrazones is deprotonated selectively, leading to the less substituted
311:
Importantly, the
Shapiro reaction cannot be used to synthesize 1-lithioalkenes (and the resulting functionalized derivatives), as sulfonylhydrazones derived from aldehydes undergo exclusive addition of the organolithium base to the carbon of the CâN double bond.
378:
The
Shapiro reaction has been used to generate olefins towards to complex natural products. K. Mori and coworkers wanted to determine the absolute configuration of the phytocassane group of a class of natural products called
329:
ratio of 99.4:0.6. The ratio was determined by capillary GLC analysis after conversion to the corresponding epoxides with mCPBA. The catalyst loading can be reduced to 0.05 equivalents in the case of a 30mmol scale reaction.
333:
The high stereoselectivity is obtained by the preferential abstraction of the α-methylene hydrogen syn to the phenylaziridine, and is also accounted for by the internal chelation of the lithiated intermediated.
436:; Lipton, M. F.; Kolonko, K. J.; Buswell, R. L.; Capuano, L. A. (1975). "Tosylhydrazones and alkyllithium reagents: More on the regiospecificity of the reaction and the trapping of three intermediates".
259:
The reaction's directionality is controlled by the stereochemistry of the hydrazone, with deprotonation occurring cis to the tosylamide group. This is due to coordination by the nitrogen atom.
358:
to produce a variety of olefin products. Keay and coworkers have developed methodology that combines these reactions in a one pot process that does not require the isolation of the
362:, a setback of the traditional Suzuki coupling. This reaction has a wide scope, tolerating a slew of trisylhydrazones and aryl halides, as well as several solvents and Pd sources.
365:
345:-aziridinylhydrazones produces the alkene product, as well as stryrene and gaseous nitrogen as byproducts. The cycle of the catalytic Shapiro reaction is also shown.
307:(1) through the intermediate hydrazone (2) to the vinyllithium (3). Addition of water (c) results in 2-bornene (4) and addition of an alkyl bromide (d) gives 5
394:
833:
Yajima, Arata; Mori, Kenji (2000). "Synthesis and absolute configuration of (â)-phytocassane D, a diterpene phytoalexin isolated from the rice plant,
1319:
71:
391:. On the way to (â)-phytocassane D, a tricyclic ketone was subjected to Shapiro reaction conditions to yield the cyclic alkene product.
1137:
851:
536:; Heath, Marsha J. (1967). "Tosylhydrazones. V. Reaction of Tosylhydrazones with Alkyllithium Reagents. A New Olefin Synthesis".
646:
489:
1122:
883:
580:
1329:
1167:
252:
1324:
121:
1097:
125:
1314:
1102:
413:
56:
156:
64:
1293:
1273:
505:
Adlington, Robert M.; Barret, Anthony G. M. (1983). "Recent applications of the
Shapiro reaction".
1334:
1233:
388:
131:
1228:
1107:
745:
1152:
876:
773:
Maruoka, Keiji; Oishi, Masataka; Yamamoto, Hisashi (1991). "The
Catalytic Shapiro Reaction".
113:
1162:
1142:
1079:
572:
408:
292:. Other reactions of vinyllithium compounds include alkylation reactions with for instance
212:
8:
1132:
1112:
1083:
1070:
1223:
1197:
1127:
839:
232:
224:
192:
450:
383:. This was accomplished by preparing the naturally occurring (â)-phytocassane D from (
1263:
1187:
1177:
1147:
1088:
819:
807:
775:
711:
671:
662:
642:
606:
576:
538:
533:
485:
464:
438:
433:
117:
40:
30:
369:
The
Shapiro and Suzuki reactions are combined to yield a variety of alkene products.
1243:
1157:
869:
847:
815:
783:
755:
720:
680:
546:
515:
477:
446:
299:
281:
181:
93:
1283:
1253:
1182:
507:
355:
759:
706:
666:
597:
481:
262:
1278:
1268:
564:
185:
170:
1308:
1238:
1213:
1117:
724:
684:
373:
1288:
1218:
1192:
359:
293:
280:
intermediate. Although many secondary reactions exist for the vinyllithium
277:
240:
852:
10.1002/1099-0690(200012)2000:24<4079::AID-EJOC4079>3.0.CO;2-R
1248:
747:
469:
380:
216:
200:
550:
519:
1258:
1074:
787:
707:"Generation and Reactions of Alkenyllithium Reagents: 2-Butylbornene"
349:
208:
174:
109:
906:
149:
128:, which also involves the basic decomposition of tosyl hydrazones.
101:
705:
Chamberlin, A. Richard; Liotta, Ellen L.; Bond, F. Thomas (1983).
398:
Use of the
Shapiro reaction in the synthesis of (â)-phytocassane D
991:
957:
923:
304:
1092:
1042:
1025:
1008:
974:
940:
892:
596:
Friedman, Lester; Litle, Robert L.; Reichle, Walter R. (1960).
289:
145:
105:
97:
266:
Intermediate explaining directionality of the
Shapiro reaction
667:"2-Bornene (1,7,7-Trimethylbicyclo[2.2.1]hept-2-ene)"
285:
220:
432:
861:
569:
Classics in Total
Synthesis: Targets, Strategies, Methods
374:
An application of the Shapiro reaction in total synthesis
639:
Intermediate Organic Chemistry--Reactions and Mechanisms
243:, including simple neutralization with water or an acid
139:
801:
Passafaro, Marco S.; Keay, Brian A. (1996). "A one pot
641:] (in Chinese) (2nd ed.). pp. 279â280.
772:
704:
595:
354:The Shapiro reaction can also be combined with the
350:A one pot in situ combined Shapiro-Suzuki reaction
1306:
563:
744:
504:
144:In a prelude to the actual Shapiro reaction, a
120:in 1967. The Shapiro reaction was used in the
877:
800:
661:
315:
532:
884:
870:
832:
288:is added, resulting in protonation to the
239:, which can then be reacted with various
467:(1976). "Alkenes from Tosylhydrazones".
298:
284:, in the Shapiro reaction in particular
261:
463:
231:. This diazonium anion is then lost as
124:. This reaction is very similar to the
1307:
865:
140:Reaction mechanism and directionality
1320:Carbon-carbon bond forming reactions
235:resulting in a vinyllithium species
112:in the presence of 2 equivalents of
805:combined Shapiro-Suzuki reaction".
13:
393:
364:
336:
211:. The carbanion then undergoes an
130:
14:
1346:
203:proton α to the hydrazone carbon
116:. The reaction was discovered by
1138:HornerâWadsworthâEmmons reaction
303:Shapiro reactions starting from
251:
826:
794:
766:
738:
698:
655:
626:
589:
557:
526:
498:
457:
426:
169:-toluenesulfonylhydrazone (or
122:Nicolaou Taxol total synthesis
1:
1123:CoreyâWinter olefin synthesis
632:
451:10.1016/S0040-4039(00)75263-4
419:
820:10.1016/0040-4039(95)02210-4
567:; Sorensen, Erik J. (1996).
180:. Two equivalents of strong
90:tosylhydrazone decomposition
7:
891:
760:10.1002/0471264180.or039.01
621:, vol. 5, p. 1055
482:10.1002/0471264180.or023.03
402:
10:
1351:
602:-Toluenesulfonylhydrazide"
341:The Shapiro reaction with
316:Catalytic Shapiro reaction
215:producing a carbonâcarbon
1294:Friedel-Crafts Alkylation
1206:
1168:RambergâBĂ€cklund reaction
1063:
899:
733:, vol. 7, p. 77
160:-toluenesulfonylhydrazide
78:
52:Organic Chemistry Portal
46:
21:
1098:BamfordâStevens reaction
725:10.15227/orgsyn.061.0141
685:10.15227/orgsyn.051.0066
665:; Duncan, J. H. (1971).
270:
126:BamfordâStevens reaction
108:through an intermediate
1330:Organic redox reactions
1234:Oxymercuration reaction
1103:BartonâKellogg reaction
414:WolffâKishner reduction
389:Wieland-Miescher ketone
1229:Electrophilic addition
1108:Boord olefin synthesis
399:
370:
346:
308:
267:
136:
1325:Olefination reactions
1153:Kauffmann olefination
565:Nicolaou, Kyriacos C.
397:
368:
340:
302:
265:
199:followed by the less
134:
114:organolithium reagent
1274:DielsâAlder reaction
1163:Peterson olefination
1143:Hydrazone iodination
1080:Dehydration reaction
445:(22â23): 1811â1814.
409:Hydrazone iodination
213:elimination reaction
135:The Shapiro reaction
1133:Hofmann elimination
1113:Chugaev elimination
1071:Dehydrohalogenation
551:10.1021/ja00998a601
520:10.1021/ar00086a004
195:from the hydrazone
104:is converted to an
1315:Coupling reactions
1198:Cope rearrangement
1128:Grieco elimination
840:Eur. J. Org. Chem.
534:Shapiro, Robert H.
465:Shapiro, Robert H.
400:
371:
347:
309:
268:
233:molecular nitrogen
137:
1302:
1301:
1264:Hydrohalogenation
1188:Olefin metathesis
1178:Takai olefination
1148:Julia olefination
1089:Semihydrogenation
846:(24): 4079â4091.
808:Tetrahedron Lett.
788:10.1021/ja951422p
776:J. Am. Chem. Soc.
731:Collected Volumes
712:Organic Syntheses
691:Collected Volumes
672:Organic Syntheses
648:978-7-04-058063-1
619:Collected Volumes
607:Organic Syntheses
545:(22): 5734â5735.
539:J. Am. Chem. Soc.
439:Tetrahedron Lett.
223:anion, forming a
219:and ejecting the
118:Robert H. Shapiro
82:
81:
41:Coupling reaction
31:Robert H. Shapiro
22:Shapiro reaction
1342:
1244:Cyclopropanation
1173:Shapiro reaction
1158:McMurry reaction
1055:
1038:
1021:
1004:
987:
970:
953:
936:
919:
886:
879:
872:
863:
862:
856:
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830:
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792:
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782:(9): 2289â2290.
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523:
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430:
282:functional group
255:
155:is reacted with
94:organic reaction
86:Shapiro reaction
74:
59:
57:shapiro-reaction
19:
18:
16:Organic reaction
1350:
1349:
1345:
1344:
1343:
1341:
1340:
1339:
1305:
1304:
1303:
1298:
1284:Dehydrogenation
1254:Dihydroxylation
1202:
1183:Wittig reaction
1059:
1054:
1050:
1046:
1037:
1033:
1029:
1020:
1016:
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508:Acc. Chem. Res.
503:
499:
492:
462:
458:
431:
427:
422:
405:
376:
356:Suzuki reaction
352:
318:
273:
142:
70:
55:
17:
12:
11:
5:
1348:
1338:
1337:
1335:Name reactions
1332:
1327:
1322:
1317:
1300:
1299:
1297:
1296:
1291:
1286:
1281:
1279:Wacker process
1276:
1271:
1269:Polymerization
1266:
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912:
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901:
897:
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889:
888:
881:
874:
866:
858:
857:
825:
814:(4): 429â432.
793:
765:
737:
697:
663:Shapiro, R. H.
654:
647:
625:
588:
581:
556:
525:
497:
491:978-0471264187
490:
476:(3): 405â507.
456:
434:Shapiro, R. H.
424:
423:
421:
418:
417:
416:
411:
404:
401:
375:
372:
351:
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317:
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256:
171:tosylhydrazone
141:
138:
80:
79:
76:
75:
68:
61:
60:
53:
49:
48:
44:
43:
38:
37:Reaction type
34:
33:
28:
24:
23:
15:
9:
6:
4:
3:
2:
1347:
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1245:
1242:
1240:
1239:Hydroboration
1237:
1235:
1232:
1230:
1227:
1225:
1222:
1220:
1217:
1215:
1214:Hydrogenation
1212:
1211:
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1205:
1199:
1196:
1194:
1191:
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1184:
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1134:
1131:
1129:
1126:
1124:
1121:
1119:
1118:Cope reaction
1116:
1114:
1111:
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761:
757:
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750:
749:
741:
732:
726:
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718:
714:
713:
708:
701:
693:, vol. 6
692:
686:
682:
678:
674:
673:
668:
664:
658:
650:
644:
640:
636:
635:äžçș§ææșććŠ--ććșäžæșç
629:
620:
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609:
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603:
601:
592:
584:
582:9783527292318
578:
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367:
363:
361:
357:
344:
339:
335:
331:
328:
324:
313:
306:
301:
297:
295:
294:alkyl halides
291:
287:
283:
279:
264:
260:
254:
250:
249:
248:
246:
242:
241:electrophiles
238:
234:
230:
226:
222:
218:
214:
210:
206:
202:
198:
194:
191:abstract the
190:
189:-butyllithium
188:
183:
179:
176:
173:) which is a
172:
168:
164:
161:
159:
154:
151:
147:
133:
129:
127:
123:
119:
115:
111:
107:
103:
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87:
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73:
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63:
62:
58:
54:
51:
50:
45:
42:
39:
36:
35:
32:
29:
26:
25:
20:
1289:Ene reaction
1219:Halogenation
1193:Ene reaction
1172:
1064:Preparations
843:
838:
835:Oryza sativa
834:
828:
811:
806:
802:
796:
779:
774:
768:
751:
746:
740:
730:
716:
710:
700:
690:
676:
670:
657:
638:
634:
628:
618:
611:
605:
599:
591:
568:
559:
542:
537:
528:
514:(2): 55â59.
511:
506:
500:
473:
468:
459:
442:
437:
428:
384:
381:phytoalexins
377:
360:boronic acid
353:
342:
332:
326:
322:
319:
310:
278:vinyllithium
274:
258:
244:
236:
228:
207:, forming a
204:
196:
186:
177:
166:
162:
157:
152:
143:
89:
85:
83:
72:RXNO:0000125
67:ontology ID
47:Identifiers
27:Named after
1249:Epoxidation
754:(1): 1â83.
748:Org. React.
470:Org. React.
217:double bond
96:in which a
1309:Categories
1259:Ozonolysis
1075:haloalkane
420:References
165:to form a
1224:Hydration
1207:Reactions
225:diazonium
209:carbanion
175:hydrazone
110:hydrazone
403:See also
184:such as
150:aldehyde
102:aldehyde
1084:alcohol
992:Heptene
958:Pentene
924:Propene
900:Alkenes
893:Alkenes
803:in situ
719:: 141.
305:camphor
1093:alkyne
1043:Decene
1026:Nonene
1009:Octene
975:Hexene
941:Butene
907:Ethene
679:: 66.
645:
633:ć, è.
579:
488:
290:alkene
227:anion
201:acidic
193:proton
148:or an
146:ketone
106:alkene
98:ketone
92:is an
1091:from
1082:from
1073:from
637:[
573:Wiley
327:trans
286:water
271:Scope
221:tosyl
844:2000
643:ISBN
614:: 93
577:ISBN
486:ISBN
182:base
84:The
848:doi
837:".
816:doi
784:doi
780:118
756:doi
721:doi
681:doi
547:doi
516:doi
478:doi
447:doi
323:cis
245:(8)
237:(7)
229:(6)
205:(5)
197:(4)
178:(3)
163:(2)
153:(1)
100:or
88:or
65:RSC
1311::
1053:20
1049:10
1036:18
1019:16
1002:14
985:12
968:10
812:37
752:39
728:;
717:61
715:.
709:.
688:;
677:51
675:.
669:.
616:;
612:40
610:.
604:.
575:.
571:.
543:89
512:16
484:.
474:23
443:16
387:)-
296:.
247:.
1056:)
1051:H
1047:C
1045:(
1039:)
1034:H
1032:9
1030:C
1028:(
1022:)
1017:H
1015:8
1013:C
1011:(
1005:)
1000:H
998:7
996:C
994:(
988:)
983:H
981:6
979:C
977:(
971:)
966:H
964:5
962:C
960:(
954:)
951:8
949:H
947:4
945:C
943:(
937:)
934:6
932:H
930:3
928:C
926:(
920:)
917:4
915:H
913:2
911:C
909:(
885:e
878:t
871:v
854:.
850::
822:.
818::
790:.
786::
762:.
758::
735:.
723::
695:.
683::
651:.
623:.
600:p
598:"
585:.
553:.
549::
522:.
518::
494:.
480::
453:.
449::
385:R
343:N
325::
187:n
167:p
158:p
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