247:
24:
640:
655:
544:
371:
630:
In what is essentially the reverse of step two, the electrons push back in the opposite direction forming a new bond between the substrate carbon and another atom. (In the case of the decarboxylases, this creates a new carbon-hydrogen bond. In the case of transketolase, this attacks a new substrate
590:. Normally, reactions that form carbanions are highly unfavorable, but the positive charge on the tetravalent nitrogen just adjacent to the carbanion stabilizes the negative charge, making the reaction much more favorable. A compound with positive and negative charges on adjacent atoms is called an
626:
The target bond on the substrate is broken, and its electrons are pushed towards the TPP. This creates a double bond between the substrate carbon and the TPP carbon and pushes the electrons in the N-C double bond in TPP entirely onto the nitrogen atom, reducing it from a positive to neutral
669:
602:
In several reactions, including that of pyruvate dehydrogenase, alpha-ketoglutarate dehydrogenase, and transketolase, TPP catalyses the reversible decarboxylation reaction (aka cleavage of a substrate compound at a carbon-carbon bond connecting a
460:
and is required in the cytosol for the activity of transketolase and in the mitochondria for the activity of pyruvate-, oxoglutarate- and branched chain keto acid dehydrogenases. To date, the yeast ThPP carrier (Tpc1p) the human Tpc and the
836:
Lindhurst, Marjorie J.; Fiermonte, Giuseppe; Song, Shiwei; Struys, Eduard; Leonardis, Francesco De; Schwartzberg, Pamela L.; Chen, Amy; Castegna, Alessandra; Verhoeven, Nanda (2006-10-24).
787:
Iacopetta, Domenico; Carrisi, Chiara; De
Filippis, Giuseppina; Calcagnile, Valeria M.; Cappello, Anna R.; Chimento, Adele; Curcio, Rosita; Santoro, Antonella; Vozza, Angelo (2010-03-01).
384:
270:
InChI=1S/C12H17N4OS.ClH.H4O7P2/c1-8-11(3-4-17)18-7-16(8)6-10-5-14-9(2)15-12(10)13;;1-8(2,3)7-9(4,5)6/h5,7,17H,3-4,6H2,1-2H3,(H2,13,14,15);1H;(H2,1,2,3)(H2,4,5,6)/q+1;;/p-1
280:
InChI=1/C12H17N4OS.ClH.H4O7P2/c1-8-11(3-4-17)18-7-16(8)6-10-5-14-9(2)15-12(10)13;;1-8(2,3)7-9(4,5)6/h5,7,17H,3-4,6H2,1-2H3,(H2,13,14,15);1H;(H2,1,2,3)(H2,4,5,6)/q+1;;/p-1
94:
931:
296:
1149:
1145:
1286:
1078:
521:
1032:
994:
915:
945:
1051:
1141:
1137:
634:
In what is essentially the reverse of step one, the TPP-substrate bond is broken, reforming the TPP ylid and the substrate carbonyl.
515:
261:
838:"Knockout of Slc25a19 causes mitochondrial thiamine pyrophosphate depletion, embryonic lethality, CNS malformations, and anemia"
1205:
1071:
1498:
467:
have been identified as being responsible for the mitochondrial transport of ThPP and ThMP. It was first discovered as an
391:
527:
204:
1127:
225:
171:
578:. Thus, the thiazole ring is the "reagent portion" of the molecule. The C2 of this ring is capable of acting as an
1064:
476:
1358:
442:
165:
789:"The biochemical properties of the mitochondrial thiamine pyrophosphate carrier from Drosophila melanogaster"
1371:
1263:
1090:
463:
446:
1271:
570:
The part of TPP molecule that is most commonly involved in reactions is the thiazole ring, which contains
506:
500:
435:
1281:
1276:
1123:
974:
36:
1488:
1189:
849:
732:"Identification and reconstitution of the yeast mitochondrial transporter for thiamine pyrophosphate"
510:
730:
Marobbio, C. M. T.; Vozza, A.; Harding, M.; Bisaccia, F.; Palmieri, F.; Walker, J. E. (2002-11-01).
1363:
1169:
623:
the carbonyl group on the substrate. (This forms a single bond between the TPP and the substrate.)
620:
612:
242:
60:
1483:
1478:
1385:
949:
925:
639:
468:
1024:
1493:
1456:
1215:
1197:
1028:
990:
911:
885:
867:
818:
810:
769:
751:
712:
134:
1016:
982:
875:
857:
800:
759:
743:
564:
486:
319:
973:
Begley, Tadhg P.; Ealick, Steven E. (2010-01-01), Liu, Hung-Wen (Ben); Mander, Lew (eds.),
668:
213:
1219:
608:
70:
853:
246:
1235:
880:
837:
683:
604:
362:
114:
764:
731:
1472:
1348:
1301:
1253:
1017:
986:
805:
788:
560:
532:
23:
1353:
1343:
1311:
450:
193:
1338:
1291:
1418:
1306:
1296:
1159:
552:
350:
125:
906:
Pavia, Donald L., Gary M. Lampman, George S. Kritz, Randall G. Engel (2006).
871:
814:
755:
594:, so sometimes the carbanion form of TPP is referred to as the "ylide form".
1413:
1408:
1243:
1229:
862:
654:
587:
889:
822:
773:
747:
716:
571:
556:
493:
482:
427:
1449:
1393:
1105:
479:
472:
457:
180:
543:
1423:
1398:
1332:
1328:
1324:
1320:
1179:
1087:
583:
575:
449:
that is present in all living systems, in which it catalyzes several
439:
40:
2--4-methyl-1,3-thiazol-3-ium-5-yl]ethyl phosphono hydrogen phosphate
361:
Except where otherwise noted, data are given for materials in their
1056:
154:
591:
542:
105:
93:
83:
1428:
1403:
1316:
646:
579:
145:
1060:
645:
The TPP thiazolium ring can be deprotonated at C2 to become an
667:
663:
A full view of TPP. The arrow indicates the acidic proton.
653:
230:
908:
Introduction to
Organic Laboratory Techniques (4th Ed.)
379:
485:, which results from a deficiency of thiamine in the
1441:
1384:
1262:
1104:
1097:
1015:Voet, Donald; Judith Voet; Charlotte Pratt (2008).
192:
842:Proceedings of the National Academy of Sciences
69:
1072:
456:Thiamine pyrophosphate is synthesized in the
304:Cc2ncc(C1csc(CCOP(=O)(O)OP(=O)(O)O)c1C)c(N)n2
8:
930:: CS1 maint: multiple names: authors list (
631:molecule to form a new carbon-carbon bond.)
1101:
1079:
1065:
1057:
948:. Georgia State University. Archived from
245:
133:
15:
879:
861:
804:
763:
615:). It achieves this in four basic steps:
212:
607:to an adjacent reactive group—usually a
910:. Thomson Brooks/Cole. pp. 304–5.
901:
899:
695:
522:Branched-chain amino acid dehydrogenase
301:
266:
241:
170:
981:, Oxford: Elsevier, pp. 547–559,
923:
559:ring, which is in turn connected to a
496:in many enzymatic reactions, such as:
475:) in humans through its link with the
1023:. John Wiley & Sons Inc. p.
273:Key: NBSUTVXQOGUTJX-UHFFFAOYSA-M
113:
7:
968:
966:
283:Key: NBSUTVXQOGUTJX-REWHXWOFAB
183:
153:
14:
979:Comprehensive Natural Products II
516:Alpha-ketoglutarate dehydrogenase
987:10.1016/b978-008045382-8.00148-9
806:10.1111/j.1742-4658.2009.07550.x
638:
369:
22:
365:(at 25 °C , 100 kPa).
355:425.314382 g/mol
619:The carbanion of the TPP ylid
551:Chemically, TPP consists of a
445:. Thiamine pyrophosphate is a
1:
975:"7.15 - Thiamin Biosynthesis"
555:ring which is connected to a
1019:Fundamentals of Biochemistry
528:2-hydroxyphytanoyl-CoA lyase
1515:
477:peripheral nervous system
438:which is produced by the
359:
312:
292:
257:
53:
45:
35:
30:
21:
621:nucleophilically attacks
547:The "ylide form" of TPP.
443:thiamine diphosphokinase
946:"PDBs for Biochemistry"
863:10.1073/pnas.0607661103
703:Pietrzak I (1995). "".
464:Drosophila melanogaster
17:Thiamine pyrophosphate
672:
658:
548:
507:Pyruvate decarboxylase
501:Pyruvate dehydrogenase
404:Thiamine pyrophosphate
172:Thiamine+pyrophosphate
671:
657:
546:
1499:Pyrophosphate esters
748:10.1093/emboj/cdf583
511:ethanol fermentation
416:thiamine diphosphate
48:Thiamine diphosphate
854:2006PNAS..10315927L
848:(43): 15927–15932.
598:Reaction mechanisms
18:
705:Przegla̧d Lekarski
673:
659:
549:
469:essential nutrient
392:Infobox references
16:
1466:
1465:
1437:
1436:
1034:978-0-470-12930-2
996:978-0-08-045382-8
917:978-0-495-28069-9
742:(21): 5653–5661.
400:Chemical compound
398:
397:
226:CompTox Dashboard
95:Interactive image
1506:
1102:
1081:
1074:
1067:
1058:
1039:
1038:
1022:
1012:
1006:
1005:
1004:
1003:
970:
961:
960:
958:
957:
942:
936:
935:
929:
921:
903:
894:
893:
883:
865:
833:
827:
826:
808:
799:(5): 1172–1181.
784:
778:
777:
767:
736:The EMBO Journal
727:
721:
720:
700:
642:
582:by donating its
565:functional group
382:
376:
373:
372:
320:Chemical formula
250:
249:
234:
232:
216:
196:
185:
174:
157:
137:
117:
97:
73:
26:
19:
1514:
1513:
1509:
1508:
1507:
1505:
1504:
1503:
1469:
1468:
1467:
1462:
1433:
1380:
1375:
1367:
1258:
1249:
1241:
1225:
1211:
1201:
1193:
1185:
1175:
1165:
1155:
1133:
1119:
1093:
1085:
1048:
1043:
1042:
1035:
1014:
1013:
1009:
1001:
999:
997:
972:
971:
964:
955:
953:
944:
943:
939:
922:
918:
905:
904:
897:
835:
834:
830:
786:
785:
781:
729:
728:
724:
702:
701:
697:
692:
680:
609:carboxylic acid
600:
541:
492:TPP works as a
433:
401:
394:
389:
388:
387: ?)
378:
374:
370:
366:
344:
340:
336:
332:
328:
322:
308:
305:
300:
299:
288:
285:
284:
281:
275:
274:
271:
265:
264:
253:
235:
228:
219:
199:
186:
160:
140:
120:
100:
87:
76:
63:
49:
41:
12:
11:
5:
1512:
1510:
1502:
1501:
1496:
1491:
1486:
1481:
1471:
1470:
1464:
1463:
1461:
1460:
1445:
1443:
1439:
1438:
1435:
1434:
1432:
1431:
1426:
1421:
1416:
1411:
1406:
1401:
1396:
1390:
1388:
1382:
1381:
1379:
1378:
1373:
1369:
1365:
1361:
1356:
1351:
1346:
1341:
1336:
1314:
1309:
1304:
1299:
1294:
1289:
1284:
1279:
1274:
1268:
1266:
1260:
1259:
1257:
1256:
1251:
1247:
1239:
1233:
1227:
1223:
1213:
1209:
1199:
1191:
1187:
1183:
1177:
1173:
1167:
1163:
1157:
1153:
1135:
1131:
1121:
1117:
1110:
1108:
1099:
1095:
1094:
1086:
1084:
1083:
1076:
1069:
1061:
1055:
1054:
1047:
1046:External links
1044:
1041:
1040:
1033:
1007:
995:
962:
937:
916:
895:
828:
779:
722:
694:
693:
691:
688:
687:
686:
684:TPP riboswitch
679:
676:
675:
674:
661:
660:
636:
635:
632:
628:
624:
605:carbonyl group
599:
596:
586:and forming a
563:(diphosphate)
540:
537:
536:
535:
530:
525:
519:
513:
504:
431:
399:
396:
395:
390:
368:
367:
363:standard state
360:
357:
356:
353:
347:
346:
342:
338:
334:
330:
326:
323:
318:
315:
314:
310:
309:
307:
306:
303:
295:
294:
293:
290:
289:
287:
286:
282:
279:
278:
276:
272:
269:
268:
260:
259:
258:
255:
254:
252:
251:
238:
236:
224:
221:
220:
218:
217:
209:
207:
201:
200:
198:
197:
189:
187:
179:
176:
175:
168:
162:
161:
159:
158:
150:
148:
142:
141:
139:
138:
130:
128:
122:
121:
119:
118:
110:
108:
102:
101:
99:
98:
90:
88:
81:
78:
77:
75:
74:
66:
64:
59:
56:
55:
51:
50:
47:
43:
42:
39:
33:
32:
28:
27:
13:
10:
9:
6:
4:
3:
2:
1511:
1500:
1497:
1495:
1492:
1490:
1487:
1485:
1482:
1480:
1477:
1476:
1474:
1459:
1458:
1452:
1451:
1447:
1446:
1444:
1440:
1430:
1427:
1425:
1422:
1420:
1417:
1415:
1412:
1410:
1407:
1405:
1402:
1400:
1397:
1395:
1392:
1391:
1389:
1387:
1383:
1377:
1370:
1368:
1362:
1360:
1357:
1355:
1352:
1350:
1349:Molybdopterin
1347:
1345:
1342:
1340:
1337:
1334:
1330:
1326:
1322:
1318:
1315:
1313:
1310:
1308:
1305:
1303:
1302:Cofactor F430
1300:
1298:
1295:
1293:
1290:
1288:
1285:
1283:
1280:
1278:
1275:
1273:
1270:
1269:
1267:
1265:
1261:
1255:
1254:Coenzyme F420
1252:
1245:
1237:
1236:Phylloquinone
1234:
1231:
1230:Ascorbic acid
1228:
1221:
1217:
1214:
1207:
1203:
1195:
1188:
1181:
1178:
1171:
1168:
1161:
1158:
1151:
1147:
1143:
1139:
1136:
1129:
1125:
1122:
1115:
1112:
1111:
1109:
1107:
1103:
1100:
1096:
1092:
1089:
1082:
1077:
1075:
1070:
1068:
1063:
1062:
1059:
1053:
1050:
1049:
1045:
1036:
1030:
1026:
1021:
1020:
1011:
1008:
998:
992:
988:
984:
980:
976:
969:
967:
963:
952:on 2011-07-16
951:
947:
941:
938:
933:
927:
919:
913:
909:
902:
900:
896:
891:
887:
882:
877:
873:
869:
864:
859:
855:
851:
847:
843:
839:
832:
829:
824:
820:
816:
812:
807:
802:
798:
794:
790:
783:
780:
775:
771:
766:
761:
757:
753:
749:
745:
741:
737:
733:
726:
723:
718:
714:
711:(10): 522–5.
710:
707:(in Polish).
706:
699:
696:
689:
685:
682:
681:
677:
670:
666:
665:
664:
656:
652:
651:
650:
648:
643:
641:
633:
629:
625:
622:
618:
617:
616:
614:
610:
606:
597:
595:
593:
589:
585:
581:
577:
573:
568:
566:
562:
561:pyrophosphate
558:
554:
545:
538:
534:
533:Transketolase
531:
529:
526:
523:
520:
517:
514:
512:
508:
505:
502:
499:
498:
497:
495:
490:
488:
484:
481:
478:
474:
470:
466:
465:
459:
454:
452:
448:
444:
441:
437:
429:
425:
424:cocarboxylase
421:
417:
413:
409:
405:
393:
386:
381:
364:
358:
354:
352:
349:
348:
324:
321:
317:
316:
311:
302:
298:
291:
277:
267:
263:
256:
248:
244:
243:DTXSID2048404
240:
239:
237:
227:
223:
222:
215:
211:
210:
208:
206:
203:
202:
195:
191:
190:
188:
182:
178:
177:
173:
169:
167:
164:
163:
156:
152:
151:
149:
147:
144:
143:
136:
132:
131:
129:
127:
124:
123:
116:
112:
111:
109:
107:
104:
103:
96:
92:
91:
89:
85:
80:
79:
72:
68:
67:
65:
62:
58:
57:
52:
44:
38:
34:
29:
25:
20:
1454:
1448:
1354:Mycofactocin
1344:Methanofuran
1264:non-vitamins
1113:
1098:Active forms
1018:
1010:
1000:, retrieved
978:
954:. Retrieved
950:the original
940:
907:
845:
841:
831:
796:
793:FEBS Journal
792:
782:
739:
735:
725:
708:
704:
698:
662:
644:
637:
601:
569:
550:
491:
462:
455:
423:
419:
415:
411:
407:
403:
402:
54:Identifiers
46:Other names
1489:Pyrimidines
1339:Lipoic Acid
1317:Heme / Haem
1244:Menaquinone
453:reactions.
451:biochemical
313:Properties
1473:Categories
1442:Base forms
1386:metal ions
1312:Coenzyme Q
1307:Coenzyme M
1297:Coenzyme B
1160:Coenzyme A
1114:TPP / ThDP
1002:2020-12-16
956:2009-02-07
690:References
553:pyrimidine
436:derivative
430:(vitamin B
351:Molar mass
214:Q57971654Y
126:ChemSpider
115:CHEBI:9532
82:3D model (
61:CAS Number
37:IUPAC name
1484:Thiazoles
1479:Cofactors
1372:THMPT / H
1170:PLP / P5P
1091:cofactors
926:cite book
872:0027-8424
815:1742-4658
756:0261-4189
588:carbanion
539:Chemistry
1494:Thiamine
1457:vitamins
1450:vitamins
1364:THB / BH
1198:DHFA / H
1190:THFA / H
1106:vitamins
890:17035501
823:20121944
774:12411483
678:See also
572:nitrogen
557:thiazole
494:coenzyme
483:beriberi
447:cofactor
428:thiamine
345:S
135:10670483
71:136-08-3
1052:UIC.edu
881:1595310
850:Bibcode
717:8834846
613:alcohol
524:complex
518:complex
503:complex
480:disease
473:vitamin
458:cytosol
385:what is
383: (
181:PubChem
1404:Fe, Fe
1216:AdoCbl
1180:Biotin
1088:Enzyme
1031:
993:
914:
888:
878:
870:
821:
813:
772:
765:131080
762:
754:
715:
611:or an
584:proton
576:sulfur
440:enzyme
422:), or
414:), or
380:verify
377:
297:SMILES
155:C00068
31:Names
1220:MeCbl
1150:NADPH
627:form.
592:ylide
426:is a
262:InChI
106:ChEBI
84:JSmol
1455:see
1287:PAPS
1282:SAMe
1206:MTHF
1146:NADP
1142:NADH
1029:ISBN
991:ISBN
932:link
912:ISBN
886:PMID
868:ISSN
819:PMID
811:ISSN
770:PMID
752:ISSN
713:PMID
647:ylid
580:acid
574:and
487:diet
420:ThDP
412:ThPP
205:UNII
194:1132
166:MeSH
146:KEGG
1376:MPT
1359:PQQ
1292:GSH
1277:CTP
1272:ATP
1242:),
1232:(C)
1138:NAD
1128:FAD
1124:FMN
1025:508
983:doi
876:PMC
858:doi
846:103
801:doi
797:277
760:PMC
744:doi
509:in
410:or
408:TPP
231:EPA
184:CID
1475::
1453::
1429:Zn
1424:Ni
1419:Mo
1414:Mn
1409:Mg
1399:Cu
1394:Ca
1331:,
1327:,
1323:,
1246:(K
1238:(K
1224:12
1222:(B
1218:,
1208:(B
1204:,
1202:FA
1196:,
1194:FA
1182:(B
1172:(B
1162:(B
1152:(B
1148:,
1144:,
1140:,
1130:(B
1126:,
1116:(B
1027:.
989:,
977:,
965:^
928:}}
924:{{
898:^
884:.
874:.
866:.
856:.
844:.
840:.
817:.
809:.
795:.
791:.
768:.
758:.
750:.
740:21
738:.
734:.
709:52
649::
567:.
489:.
434:)
331:19
327:12
1374:4
1366:4
1335:)
1333:O
1329:C
1325:B
1321:A
1319:(
1250:)
1248:2
1240:1
1226:)
1212:)
1210:9
1200:2
1192:4
1186:)
1184:7
1176:)
1174:6
1166:)
1164:5
1156:)
1154:3
1134:)
1132:2
1120:)
1118:1
1080:e
1073:t
1066:v
1037:.
985::
959:.
934:)
920:.
892:.
860::
852::
825:.
803::
776:.
746::
719:.
471:(
432:1
418:(
406:(
375:Y
343:2
341:P
339:7
337:O
335:4
333:N
329:H
325:C
233:)
229:(
86:)
Text is available under the Creative Commons Attribution-ShareAlike License. Additional terms may apply.
