170:
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476:
574:
404:
262:
279:
Phosphorus ylides are important reagents in organic chemistry, especially in the synthesis of naturally occurring products with biological and pharmacological activities. Much of the interest in the coordination properties of a-keto stabilized phosphorus ylides stems from their coordination
176:
The actual bonding picture of these types of ylides is strictly zwitterionic (the structure on the right) with the strong
Coulombic attraction between the "onium" atom and the adjacent carbon accounting for the reduced bond length. Consequently, the carbon anion is trigonal pyramidal.
756:"Synthesis, characterization, thermal, electrochemical, and DFT studies of mononuclear cyclopalladated complexes containing bidentate phosphine ligands and their biological evaluation as antioxidant and antibacterial agents"
112:
with a formal positive charge (usually nitrogen, phosphorus or sulfur), and in which both atoms have full octets of electrons. The result can be viewed as a structure in which two adjacent atoms are connected by both a
501:
is often considered a titanium ylide. Like the Wittig reagent, it is able to replace the oxygen atom on carbonyl groups with a methylene group. Compared with the Wittig reagent, it has more functional group tolerance.
968:
Patel, Ramesh M.; Argade, Narshinha P. (2007). "Facile SN2' Coupling
Reactions of Wittig Reagents with Dimethyl Bromomethylfumarate: Synthesis of Enes, Dienes, and Related Natural Products".
699:
630:
754:
Sabouncheia, Seyyed Javad; Ahmadi, Mohsen; Nasri, Zahra; Shams, Esmaeil; Salehzadeh, Sadegh; Gholiee, Yasin; Karamian, Roya; Asadbegy, Mostafa; Samiee, Sepideh (2013).
573:
272:
2 mechanism, a less sterically hindered alkyl halide reacts more favorably with triphenylphosphine than an alkyl halide with significant steric hindrance (such as
300:
and ylide functionalities, and can exist in ylidic and enolate forms. These ligands can therefore be engaged in different kinds of bonding with metal ions like
169:
605:
738:
276:). Because of this, there will typically be one synthetic route in a synthesis involving such compounds that is more favorable than another.
1010:
899:
Ferguson, Marcelle L.; Senecal, Todd D.; Groendyke, Todd M.; Mapp, Anna K. (2006). "-Rearrangements of
Phosphonium Ylides".
228:. Ylides can be 'stabilised' or 'non-stabilised'. A phosphonium ylide can be prepared rather straightforwardly. Typically,
755:
590:
296:, etc., viz., C(H)C(O)R and C(H)C(O)R (R = Me, Ph or OMe) constitute an important class of hybrid ligands containing both
192:
817:
787:
Padwa, Albert (2005). "Catalytic
Decomposition of Diazo Compounds as a Method for Generating Carbonyl-Ylide Dipoles".
1015:
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versatility due to the presence of different functional groups in their molecular structure.
978:
909:
873:
842:
834:
825:
818:"A metal–amide dependent, catalytic C–H functionalisation of triphenylphosphonium methylide"
798:
769:
713:
394:
122:
67:
37:
939:
659:
547:
511:
213:
201:
91:
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245:
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A [3,3]-sigmatropic reaction has been observed in certain phosphonium ylides.
1004:
970:
943:
935:
450:
157:
114:
709:
686:
561:
253:
237:
233:
403:
164:, known as the ylene form, while the actual structure lies in between both forms:
252:
salt, which can be isolated or treated in situ with a strong base (in this case,
955:
704:
419:
249:
126:
773:
665:
650:
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523:
457:
443:
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217:
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708:, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "
717:
668:: a neutral molecule with one or more pairs of positive and negative charges
535:
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301:
297:
225:
105:
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921:
885:
847:
802:
553:
439:
389:
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361:
305:
209:
97:
261:
144:
The class name "ylide" for the compound should not be confused with the
951:
862:
Sweeney, J. B. (2009). "Sigmatropic rearrangements of 'onium' ylides".
838:
655:
411:
353:
334:
205:
134:
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913:
17:
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221:
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954:) forms an ylide. (iii) A rearrangement reaction (in blue) yields a
365:
186:
293:
289:
101:
460:(RRN=N), which generally decompose by extrusion of dinitrogen.
442:
or by thermal ring opening reaction of certain N-substituted
288:
The a-keto stabilized ylides derived from bisphosphines like
938:
with 2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane forms a
816:
Nako, Adi E.; White, Andrew J. P.; Crimmin, Mark R. (2013).
49:
456:
A rather exotic family of dinitrogen-based ylides are the
453:
are known almost exclusively as unstable intermediates.
494:. After a -rearrangement, a homoallylhalide is obtained.
79:
73:
43:
568:
gas as a byproduct, and forms a silyl-stabilised ylide.
434:. These ylides can be generated by condensation of an α-
617:
Wittig reagents are found to react as nucleophiles in
530:. For instance an azomethine ylide is a dipole in the
560:, triphenylphosphonium methylide can be coupled with
82:
76:
52:
46:
70:
40:
637:The initial addition reaction is followed by an
593:is an example of a -sigmatropic reaction. The
510:An important ylide reaction is of course the
490:can be prepared from allyl halides and metal
8:
121:; normally written X–Y. Ylides are thus 1,2-
372:(RR'-O-CR'R) are formed by the reaction of
466:also have a ylidic resonance contributor,
846:
733:. Thomson Brooks/Cole. pp. 720–722.
352:(RR'C=OCRR') can form by ring-opening of
212:to alkenes. The positive charge in these
100:containing a formally negatively charged
678:
236:in a mechanism analogous to that of an
514:(for phosphorus) but there are more.
410:These compounds can be envisioned as
7:
200:Phosphonium ylides are used in the
705:Compendium of Chemical Terminology
364:, which are usually prepared from
25:
392:-based ylides also exist such as
156:Many ylides may be depicted by a
689:– via The Free Dictionary.
629:
604:
572:
474:
402:
260:
168:
66:
36:
284:Non-symmetric phosphorus ylides
1:
658:: a neutral molecule with an
591:Sommelet-Hauser rearrangement
224:substituents and a bond to a
193:methylenetriphenylphosphorane
662:cation and a negative charge
542:Dehydrocoupling with silanes
398:with the general structure:
321:Other common ylides include
232:is allowed to react with an
432:electron withdrawing groups
333:used in the preparation of
204:, a method used to convert
1032:
774:10.1016/j.crci.2012.10.006
581:Sigmatropic rearrangements
564:. This reaction produces H
528:1,3-dipolar cycloadditions
731:Organic Chemistry, 7th Ed
414:cations placed next to a
108:) directly attached to a
865:Chemical Society Reviews
449:The further-unsaturated
331:Corey-Chaykovsky reagent
718:10.1351/goldbook.Y06728
546:In the presence of the
248:forms an alkyltriphenyl
803:10.1002/hlca.200590109
790:Helvetica Chimica Acta
729:McMurry, John (2008).
613:Allylic rearrangements
518:Dipolar cycloadditions
195:
139:reactive intermediates
1011:Chemical nomenclature
761:Comptes Rendus Chimie
597:is a -rearrangement.
595:Stevens rearrangement
587:sigmatropic reactions
585:Many ylides react in
339:Stevens rearrangement
256:) to form the ylide.
190:
639:elimination reaction
329:; for instance, the
152:Resonance structures
125:, and a subclass of
497:The active form of
376:with electrophilic
360:with electrophilic
162:resonance structure
948:ethyl diazoacetate
839:10.1039/C2SC21123H
356:or by reaction of
327:sulfoxonium ylides
274:tert-butyl bromide
230:triphenylphosphine
196:
181:Phosphonium ylides
1016:Functional groups
983:10.1021/jo070728z
977:(13): 4900–4904.
914:10.1021/ja058746q
908:(14): 4576–4577.
902:J. Am. Chem. Soc.
740:978-0-495-11258-7
395:azomethine ylides
384:Based on nitrogen
131:organic chemistry
129:. They appear in
123:dipolar compounds
16:(Redirected from
1023:
995:
994:
965:
959:
934:(i) Reaction of
932:
926:
925:
896:
890:
889:
878:10.1039/b604828p
872:(4): 1027–1038.
859:
853:
852:
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826:Chemical Science
822:
813:
807:
806:
797:(6): 1357–1374.
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778:
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751:
745:
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726:
720:
697:
691:
690:
683:
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608:
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526:and interact in
522:Some ylides are
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323:sulfonium ylides
264:
220:atom with three
216:is carried by a
172:
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59:
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27:Organic compound
21:
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1025:
1024:
1022:
1021:
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1001:
1000:
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946:addition (from
940:phosphite ester
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623:2' substitution
622:
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559:
544:
520:
512:Wittig reaction
508:
499:Tebbe's reagent
488:Halonium ylides
485:
464:Stable carbenes
429:
425:
386:
350:Carbonyl ylides
347:
345:Based on oxygen
319:
317:Based on sulfur
314:
286:
271:
241:
214:Wittig reagents
208:and especially
202:Wittig reaction
183:
158:multiply bonded
154:
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833:(2): 691–695.
808:
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768:(2): 159–175.
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532:Prato reaction
519:
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484:
481:
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451:nitrile ylides
427:
423:
408:
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385:
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370:Oxonium ylides
346:
343:
318:
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313:
310:
285:
282:
269:
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246:quaternization
239:
198:
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14:
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988:
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976:
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971:J. Org. Chem.
964:
961:
957:
953:
949:
945:
944:Metal carbene
941:
937:
936:allyl alcohol
931:
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903:
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848:10044/1/15254
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191:Structure of
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19:
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782:
765:
759:
749:
730:
724:
703:
695:
681:
636:
616:
599:
584:
562:phenylsilane
545:
521:
509:
496:
487:
486:
467:
462:
455:
448:
420:substituents
409:
393:
387:
369:
349:
348:
326:
322:
320:
287:
278:
268:Due to the S
267:
254:butyllithium
234:alkyl halide
199:
175:
155:
143:
61:
31:
29:
956:phosphonate
524:1,3-dipoles
458:isodiazenes
368:compounds.
312:Other types
250:phosphonium
127:zwitterions
104:(usually a
1005:Categories
673:References
666:Zwitterion
651:1,3-dipole
551:homoleptic
536:fullerenes
492:carbenoids
444:aziridines
436:amino acid
337:or in the
242:2 reaction
218:phosphorus
160:form in a
148:"-ylide".
119:ionic bond
110:heteroatom
506:Reactions
416:carbanion
358:carbonyls
302:palladium
298:phosphine
226:carbanion
210:aldehydes
106:carbanion
991:17539690
922:16594686
886:19421580
645:See also
554:catalyst
440:aldehyde
390:nitrogen
388:Certain
378:carbenes
362:carbenes
354:epoxides
335:epoxides
306:platinum
135:reagents
115:covalent
98:molecule
952:ClFeTPP
942:. (ii)
687:"ylide"
656:Betaine
548:group 3
438:and an
412:iminium
244:. This
206:ketones
117:and an
95:dipolar
92:neutral
90:) is a
989:
920:
884:
737:
710:ylides
589:. The
418:. The
374:ethers
222:phenyl
146:suffix
18:Ylides
821:(PDF)
700:IUPAC
660:onium
534:with
483:Other
366:diazo
60:) or
32:ylide
987:PMID
950:and
918:PMID
882:PMID
735:ISBN
468:e.g.
430:are
325:and
304:and
294:dppm
290:dppe
102:atom
62:ylid
979:doi
910:doi
906:128
874:doi
843:hdl
835:doi
799:doi
770:doi
714:doi
712:".
446:.
426:, R
137:or
133:as
30:An
1007::
985:.
975:72
916:.
880:.
870:38
868:.
841:.
829:.
823:.
795:88
793:.
766:16
764:.
758:.
702:,
641:.
625::
538:.
470::
380:.
341:.
308:.
292:,
141:.
50:aɪ
993:.
981::
958:.
924:.
912::
888:.
876::
851:.
845::
837::
831:4
805:.
801::
776:.
772::
743:.
716::
621:N
619:S
566:2
558:3
556:Y
428:2
424:1
422:R
270:N
240:N
238:S
86:/
83:d
80:ɪ
77:l
74:ɪ
71:ˈ
68:/
64:(
56:/
53:d
47:l
44:ɪ
41:ˈ
38:/
34:(
20:)
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