632:
651:
690:
622:
24:
669:
408:
685:
Common byproducts of the alpha-hydroxylation tend to include overoxidation to the corresponding dicarbonyl or intermolecular aldol reaction of the starting material. Procedures to prevent side reactions include the inverse addition of the enolate to MoOPH or careful control of the temperature (-78 to
700:
679:
617:{\displaystyle {\ce {MoO3}}\xrightarrow {\stackrel {1.{\ce {H2O2}}}{2.{\ce {HMPA}}}} {\ce {MoO5 (H2O) (HMPA)}}\xrightarrow {\text{0.2 Torr}} {\ce {MoO5 (HMPA)}}\xrightarrow {\text{Pyridine}} {\ce {MoO5(HMPA)(pyridine)}}}
86:
799:"HYDROXYLATION OF ENOLATES WITH OXODIPEROXYMOLYBDENUM(PYRIDINE)(HEXAMETHYLPHOSPHORIC TRIAMIDE), MoO5·Py·HMPA(MoOPH): 3-HYDROXY-1,7,7-TRIMETHYLBICYCLOHEPTAN-2-ONE".
964:
Morizawa, Yoshitomi; Yasuda, Arata; Uchida, Keiichi (1986). "Trifluoromethyl group induced highly stereoselective synthesis of α-hydroxy carbonyl compounds".
831:
Vedejs, E.; Engler, D. A.; Telschow, J. E. (1978-01-01). "Transition-metal peroxide reactions. Synthesis of α-hydroxycarbonyl compounds from enolates".
200:
1134:
686:-20 °C). Notable miscellaneous reactions include MoOPH’s ability to oxidize alkylboranes directly to the alcohol with net stereo-retention.
631:
744:
1139:
175:
1035:
Little, R.Daniel; Myong, Sun Ok (1980). "Oxidative desulfonylation. Phenyl vinyl sulfone as a ketene synthetic equivalent".
1000:
Vedejs, E.; Telschow, J. E. (1976-02-20). "Synthesis of cyanohydrins from cyanides. Transition metal peroxide reactions".
785:
1097:
Matlin, S. A.; Sammes, P. G. (1972-01-01). "A new method for the preparation of hydroxamic acids from secondary amides".
302:
1062:
Midland, M. Mark; Preston, Scott B. (1980-10-01). "Stereochemistry of molybdenum peroxide oxidation of organoboranes".
1144:
926:
Hanessian, Stephen; Cooke, Nigel G.; DeHoff, Brad; Sakito, Yoji (1990-06-01). "The total synthesis of (+)-ionomycin".
381:
as an efficient alpha-hydroxylating agent in 1974 and an effective preparative procedure was later published in 1978.
144:
184:
InChI= 1S/C6H18N3OP.C5H5N.Mo.2O2.O/c1-7(2)11(10,8(3)4)9(5)6;1-2-4-6-5-3-1;;2*1-2;/h1-6H3;1-5H;;;;/q;;+4;2*-2;
1149:
644:
361:-containing compounds. Other reagents used for alpha-hydroxylation via enol or enolate structures include
689:
161:
643:, preferential attack at the O–O bond occurs from the less hindered enolate face in the absence of
390:
52:
1154:
754:
727:
Edwin Vedejs (April 15, 2001). "Oxodiperoxymolybdenum(pyridine)(hexamethylphosphoric triamide)".
374:
696:
MoOPH has also been shown to oxidize N-trimethylsilyl amides directly to the hydroxamic acid.
1110:
1079:
1017:
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223:
62:
766:
665:; however, in the case of branched nitriles, this reaction directly affords the ketone.
900:
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699:
675:
In the case of sulfones, alpha-hydroxylation leads directly to the ketone or aldehyde.
296:
1048:
977:
1128:
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866:
Yuan, Changxia; Jin, Yehua; Wilde, Nathan C.; Baran, Phil S. (2016-07-11).
779:
Paquette, Leo A.; and Koh
Dongsoo (14 Sep 1992). "Explosion with MoO
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402:
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939:
844:
658:
350:
322:
118:
698:
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630:
366:
868:"Short, Enantioselective Total Synthesis of Highly Oxidized Taxanes"
571:
535:
431:
295:
Except where otherwise noted, data are given for materials in their
23:
85:
75:
398:
342:
338:
319:
oxodiperoxymolybdenum(pyridine)-(hexamethylphosphoric triamide)
38:
Oxodiperoxymolybdenum(pyridine)(hexamethylphosphoric triamide)
149:
333:(VI) center with multiple oxygen ligands, coordinated with
588:
552:
509:
492:
472:
459:
423:
1099:
Journal of the
Chemical Society, Chemical Communications
289:
103–105 °C (217–221 °F; 376–378 K) (dec)
661:
with acidic alpha protons can be converted directly to
353:
and related structures, and thus can be used for alpha-
411:
616:
995:
993:
991:
989:
987:
130:
61:
729:Encyclopedia of Reagents for Organic Synthesis
635:Transition state for MoOPH alpha-hydroxylation
341:ligands, although the HMPA can be replaced by
8:
208:c0cccc012(OO1)(OO2)(=O)=P(N(C)C)(N(C)C)N(C)C
105:
15:
899:
783:-DMPU complex" (letter to the editor) in
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872:Angewandte Chemie International Edition
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160:
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722:
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377:). This reagent was first utilized by
187:Key: PPRBHGIGPWBROO-UHFFFAOYSA-N
7:
959:
957:
921:
919:
826:
824:
822:
121:
349:source of oxygen that reacts with
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241:
14:
1064:The Journal of Organic Chemistry
1002:The Journal of Organic Chemistry
833:The Journal of Organic Chemistry
244:
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22:
299:(at 25 °C , 100 kPa).
1135:Reagents for organic chemistry
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1:
1049:10.1016/s0040-4039(00)78683-7
978:10.1016/s0040-4039(00)84388-9
786:Chemical and Engineering News
1171:
389:MoOPH is synthesized from
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216:
196:
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45:
35:
30:
21:
1140:Molybdenum(VI) compounds
813:10.15227/orgsyn.064.0127
737:10.1002/047084289X.ro022
884:10.1002/anie.201602235
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135: (wrong formula)
1107:10.1039/c39720001222
409:
397:and addition of the
1076:10.1021/jo01310a054
1037:Tetrahedron Letters
1014:10.1021/jo00866a048
966:Tetrahedron Letters
940:10.1021/ja00169a041
845:10.1021/jo00396a002
590:
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391:molybdenum trioxide
271: g·mol
18:
1145:Pyridine complexes
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683:
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637:
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393:by oxidation with
375:Rubottom oxidation
303:Infobox references
16:
1070:(22): 4514–4515.
1043:(35): 3339–3342.
972:(16): 1833–1836.
934:(13): 5276–5290.
878:(29): 8280–8284.
801:Organic Syntheses
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363:Davis oxaziridine
327:organic synthesis
311:Chemical compound
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145:CompTox Dashboard
87:Interactive image
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329:. It contains a
317:, also known as
279:Yellow crystals
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224:Chemical formula
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639:Due to MoOPH's
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1008:(4): 740–741.
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807:: 127. 1986.
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789:, p. 2.
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663:cyanohydrins
656:
638:
388:
379:Edwin Vedejs
318:
314:
313:
46:Identifiers
36:Other names
641:steric bulk
371:peroxyacids
345:. It is an
276:Appearance
217:Properties
1129:Categories
707:References
647:factors.
627:Reactivity
331:molybdenum
264:Molar mass
98:ChemSpider
74:3D model (
63:23319-63-3
53:CAS Number
1155:Peroxides
1115:0022-4936
1084:0022-3263
1022:0022-3263
948:0002-7863
892:1521-3773
853:0022-3263
765:ignored (
755:cite book
405:ligands:
385:Synthesis
910:27240325
659:nitriles
607:pyridine
573:Pyridine
569:→
537:0.2 Torr
533:→
429:→
403:pyridine
359:carbonyl
351:enolates
335:pyridine
325:used in
901:4972021
323:reagent
321:, is a
132:5148822
119:PubChem
107:9743008
1113:
1082:
1020:
946:
908:
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890:
851:
743:
367:oxygen
269:434.25
201:SMILES
31:Names
17:MoOPH
373:(see
315:MoOPH
176:InChI
76:JSmol
1111:ISSN
1080:ISSN
1018:ISSN
944:ISSN
906:PMID
888:ISSN
849:ISSN
767:help
741:ISBN
596:HMPA
560:HMPA
524:HMPA
440:HMPA
401:and
399:HMPA
343:DMPU
339:HMPA
337:and
1103:doi
1072:doi
1045:doi
1010:doi
974:doi
936:doi
932:112
896:PMC
880:doi
841:doi
809:doi
733:doi
580:MoO
544:MoO
484:MoO
415:MoO
357:of
150:EPA
122:CID
1131::
1109:.
1078:.
1068:45
1066:.
1041:21
1039:.
1016:.
1006:41
1004:.
986:^
970:27
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870:.
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821:^
805:64
803:.
759::
757:}}
753:{{
739:.
731:.
715:^
446:1.
436:2.
365:,
242:Mo
239:23
233:11
1117:.
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843::
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769:)
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604:(
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563:)
557:(
548:5
527:)
521:(
516:)
513:O
505:2
501:H
497:(
488:5
468:2
464:O
455:2
451:H
419:3
257:P
254:6
251:O
248:4
245:N
236:H
230:C
152:)
148:(
78:)
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