Abstract
α-Metalated ylides, the so-called yldiides, represent a unique class of carbon-centered donor ligands. With two lone pairs of electrons at the central ylidic carbon atom, they are closely related to important organometallic ligand systems, above all bisylides and methandiides, and thus have attracted considerable research interest both from experimental and theoretical points of view. Although the number of isolated and structurally characterized yldiides is still limited, reactivity studies have demonstrated their exciting chemistry. Nowadays applications range from their use as powerful, highly nucleophilic reagents in organic synthesis such as in cascade reactions to their use as strong σ- and π-donor ligands in main group element and transition metal chemistry. The unique reactivity and donor capacity of α-metalated ylides is thereby strongly connected with the availability of the two lone pairs at the ylidic carbon atom, which makes yldiides to a special class of ylidic compounds. This review summarizes the chemistry of yldiides, particularly highlighting recent developments in their isolation and applications, also emphasizing structural and electronic properties of these compounds.
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Michaelis A, Gimborn HV (1894) Chem Ber 27:272–277
Cristau H-J (1994) Chem Rev 94:1299–1313
Wittig G, Rieber M (1949) Justus Liebigs Ann Chem 562:177–187
Schröder FG, Sundermeyer J (2015) Organometallics 34:1017–1020
Cramer RE, Bruck MA, Gilje JW (1986) Organometallics 5:1496–1499
Less RJ, Naseri V, Wright DS (2009) Organometallics 28:3594–3596
Cristau HJ, Ribeil Y (1988) J Organomet Chem 352:C51–C53
Cristau HJ, Ribeil Y, Chiche L, Plénat F (1988) J Organomet Chem 352:C47–C50
McKenna EG, Walker BJ (1988) Tetrahedron Lett 29:485–488
McKenna EG, Walker BJ (1989) J Chem Soc Chem Commun 568–569. doi: https://doi.org/10.1039/C39890000568
Taillefer M, Cristau HJ, Fruchier A, Vicente V (2001) J Organomet Chem 624:307–315
Usón R, Laguna A, Laguna M, Jiménez J, Jones PG (1991) Angew Chem 103:190–191
Schmidbaur H, Hartmann C, Reber G, Müller G (1987) Angew Chem 99:1189–1191
Basil JD, Murray HH, Fackler JP, Tocher J, Mazany AM, Trzcinska-Bancroft B, Knachel H, Dudis D, Delord TJ, Marler D (1985) J Am Chem Soc 107:6908–6915
Mohr F, Sanz S, Tiekink ERT, Laguna M (2006) Organometallics 25:3084–3087
Méndez LA, Jiménez J, Cerrada E, Mohr F, Laguna M (2005) J Am Chem Soc 127:852–853
Navarro R, Urriolabeitia EP (1999) Dalton Trans 4111–4122
Urriolabeitia EP (2008) Dalton Trans 5673–5686
Scharf LT, Gessner VG (2017) Inorg Chem 56:8599–8607
Corey EJ, Kang J (1982) J Am Chem Soc 104:4724–4725
Baumgarnter T, Schinkels B, Gudat D, Nieger M, Niecke E (1997) J Am Chem Soc 119:12410–12411
Dyker CA, Bertrand G (2009) Nat Chem 1:265–266
Schmidbaur H, Schier A (2012) Angew Chem Int Ed 52:176–186
Zhao L, Hermann M, Holzmann N, Frenking G (2017) Coord Chem Rev 344:163–204
Harder S (2011) Coord Chem Rev 255:1252–1267
Marek I (2000) Chem Rev 100:2887–2900
Green MLH (1995) J Organomet Chem 500:127–148
Jones ND, Cavell RG (2005) J Organomet Chem 690:5485–5496
Cantat T, Mézailles N, Auffrant A, Le Floch P (2008) Dalton Trans 1957–1972
Liddle ST, Mills DP, Wooles AJ (2011) Chem Soc Rev 40:2164–2176
Gessner VH, Becker J, Feichtner K-S (2015) Eur J Inorg Chem 1841–1859
Petz W (2015) Coord Chem Rev 291:1–27
Alcarazo M (2011) Dalton Trans 40:1839–1845
Alcarazo M (2017) Synthesis, structure, and reactivity of carbodiphosphoranes, carbodicarbenes, and related species. Struct Bond. https://doi.org/10.1007/430_2017_19 (this volume)
Liu S, Chen W-C, Ong T-G (2017) Synthesis and structure of carbodicarbenes and their application in catalysis. Struct Bond. https://doi.org/10.1007/430_2017_20 (this volume)
Bestmann HJ, Besold R, Sandmeier D (1975) Tetrahedron Lett 16:2293–2294
Bestmann HJ, Sandmeier D (1975) Angew Chem 87:630
Corey EJ, Kang J, Kyler K (1985) Tetrahedron Lett 26:555–558
Schaub B, Jenny T, Schlosser M (1984) Tetrahedron Lett 25:4097–4100
Schaub B, Schlosser M (1985) Tetrahedron Lett 26:1623–1626
Bestmann HJ, Schmidt M (1987) Angew Chem Int Ed Eng 26:79–81
Goumri-Magnet S, Gornitzka H, Baceiredo A, Bertrand G (1999) Angew Chem Int Ed 38:678–680
Scherpf T, Wirth R, Molitor S, Feichtner K-S, Gessner VH (2015) Angew Chem Int Ed 54:8542–8546
Hardy GE, Zink JI, Kaska WC, Baldwin JC (1978) J Am Chem Soc 100:8001–8002
Garduno-Alvia A, Lenk R, Escudié Y, González ML, Bousquet L, Saffon-Merceron N, Toledano CA, Bagan X, Branchadell V, Maerten E, Baceiredo A (2017) Eur J Inorg Chem 3494–3497
McDowell RS, Streitwieser A Jr (1984) J Am Chem Soc 106:4047–4048
Himmel D, Krossing I, Schnepf A (2014) Angew Chem Int Ed 53:370–374
Frenking G (2014) Angew Chem Int Ed 53:6040–6046
Himmel D, Krossing I, Schnepf A (2014) Angew Chem Int Ed 53:6047–6048
Lischka H (1977) J Am Chem Soc 99:353–360
Tonner R, Öxler F, Neumüller B, Petz W, Frenking G (2006) Angew Chem Int Ed 45:8038–8042
Tonner R, Frenking G (2008) Chem Eur J 14:3260–3272
Tonner R, Frenking G (2008) Chem Eur J 14:3273–3289
Tonner R, Frenking G (2009) Pure Appl Chem 81:597–614
Dewar M (1951) Bull Soc Chim Fr 18:C79
Chatt J, Duncanson LA (1953) J Chem Soc 2939–2947
Alcarazo M, Lehman CW, Anoop A, Thiel W, Fürstner A (2009) Nat Chem 1:295–301
Tonner R, Frenking G (2007) Angew Chem Int Ed 46:8695–8698
Klein S, Tonner R, Frenking G (2010) Chem Eur J 16:10160–10170
Takagi N, Tonner R, Frenking G (2012) Chem Eur J 18:1772–1780
Scharf LT, Andrada DM, Frenking G, Gessner VH (2017) Chem Eur J 23:4432–4434
Kolodiazhnyi OI (1999) Phosphorus ylides; chemistry and application in organic synthesis. Wiley-VCH, Weinheim
Maryanoff BE, Reitz AB (1989) Chem Rev 89:863–927
Byrne PA, Gilheany DG (2013) Chem Soc Rev 42:6670–6696
Bestmann HJ, Schmidt M (1987) Tetrahedron Lett 28:2111–2114
Igau A, Grützmacher H, Baceiredo A, Bertrand G (1988) J Am Chem Soc 110:6463–6466
Arduengo AJ, Harlow LM, Kine M (1991) J Am Chem Soc 113:361–363
Vignolle J, Cattoën X, Bourissou D (2009) Chem Rev 109:3333–3384
Soleilhavoup M, Bertrand G (2014) Acc Chem Res 48:256–266
Melaimi M, Soleilhavoup M, Bertrand G (2010) Angew Chem Int Ed 49:8810–8849
Rovis T, Nolan SP (2013) Synlett 24:1188–1189
Arduengo AJ, Bertrand G (2009) Chem Rev 109:3209–3210
Schuster O, Yang L, Raubenheimer HG, Albrecht M (2009) Chem Rev 109:3445–3478
Dötz KH, Stendel J (2009) Chem Rev 109:3227–3274
Wang Y, Robinson GH (2011) Inorg Chem 50:12326–12337
Bugaut X, Glorius F (2012) Chem Soc Rev 41:3511–3522
Ender D, Niemeier O, Henseler A (2007) Chem Rev 107:5606–5655
Frey GD, Lavalla V, Donnadieu B, Schoeller WW, Bertrand G (2007) Science 316:439–441
Back O, Kuchenbeiser G, Donnadieu B, Bertrand G (2009) Angew Chem Int Ed 48:5530–5533
Schmidt D, Bertel JHJ, Pietsch S, Radius U (2012) Angew Chem Int Ed 51:8881–8885
Lavigne F, Maerten E, Alcaraz G, Branchadell V, Saffon-Merceron N, Baceiredo A (2012) Angew Chem Int Ed 51:2489–2492
Facchin G, Campostrini R, Michelin RA (1985) J Organomet Chem 294:C21–C25
Michelin RA, Facchin G, Braga D, Sabatino P (1986) Organometallics 5:2265–2274
Michelin RA, Mozzon M, Facchin G, Braga D, Sabatino P (1988) J Chem Soc Dalton Trans 1803–1811
Facchin G, Mozzon M, Michelin RA, Ribeiro MTA, Pombeiro AJL (1992) J Chem Soc Dalton Trans 2827–2835
Pombeiro AJL (2005) J Organomet Chem 690:6021–6040
Nakafuji S, Kobayashi J, Kawashima T (2008) Angew Chem Int Ed 47:1141–1144
Kobayashi J, Nakafuji S, Yatabe A, Kawashima T (2008) Chem Commun 6233–6235
Fürstner A, Alcarazo M, Radkowski K, Lehmann CW (2008) Angew Chem Int Ed 47:8302–8306
Nelson DJ, Nolan SP (2013) Chem Soc Rev 42:6723–6753
Wolf S, Plenio J (2009) J Organomet Chem 694:1487–1492
Xu C, Wang Z-Q, Li Z, Wang W-Z, Hao X-Q, Fu W-J, Gong J-F, Ji B-M, Song M-P (2012) Organometallics 31:798–801
Asay M, Inoue S, Driess M (2011) Angew Chem Int Ed 50:9589–9592
Asay M, Jones C, Driess M (2011) Chem Rev 111:354–396
Schleyer PR, Maerker C, Dransfeld A, Jiao H, Hommes NJRE (1996) J Am Chem Soc 118:6317–6318
Chen Z, Wannere CS, Corminboeuf C, Puchta R, Schleyer PR (2005) Chem Rev 105:3842–3888
Schleyer PR, Jiao H, Hommes NJRE, Malkin VG, Malkina O (1997) J Am Chem Soc 119:12669–12670
Alvarado-Beltran I, Baceiredo A, Saffon-Merceron N, Branchadell V, Kato T (2016) Angew Chem Int Ed 55:16141–16144
Tolman CA (1977) Chem Rev 77:313–348
Crabtree RH (2005) The organometallic chemistry of the transition metals. Wiley, Hoboken
Guha AK, Gogoi U, Phukan AK (2013) Int J Quantum Chem 113:2471–2477
Esterhuysen C, Frenking G (2011) Chem Eur J 17:9944–9956
Fürstner A, Alcarazo M, Goddard R, Lehmann CW (2008) Angew Chem Int Ed 47:3210–3215
Alcarazo M, Suárez RM, Goddard R, Fürstner A (2010) Chem Eur J 16:9746–9749
Karni M, Apeloig Y (2012) Organometallics 31:2403–2415
Borthakur B, Silvi B, Dewhurst RD, Phukan AK (2016) J Comput Chem 37:1484–1490
Borthakur B, Phukan AK (2015) Chem Eur J 21:11603–11609
Bharadwaz P, Chetia P, Phukan AK (2017) Chem Eur J 23:9926–9936
Haerizade BN, Kassaee MZ, Zandi H, Koohi M, Ahmadi AA (2014) J Phys Org Chem 27:902–908
Melaimi M, Jazzar R, Soleilhavoup M, Bertrand G (2017) Angew Chem Int Ed 56:10046–10068
Bestmann HJ, Röder T, Bremer M, Löw D (1991) Chem Ber 124:199–202
Köster E, Rickborn B (1967) J Am Chem Soc 89:2782–2784
Piers WE, Bourke SC, Conroy KD (2005) Angew Chem Int Ed 44:5016–5036
Scherpf T, Feichtner K-S, Gessner VH (2017) Angew Chem Int Ed 56:3275–3279
Heckmann G, Plass W, Fluck E (1991) Z Anorg Allg Chem 596:139–148
Schmidbaur H, Tronich W (1968) Chem Ber 101:3545–3555
Schmidbaur H (1975) Acc Chem Res 8:62–70
Schmidbaur H, Malisch W (1970) Angew Chem Int Ed Eng 9:70–71
Schmidbaur H, Malisch W (1971) Chem Ber 104:150–159
Schmidpeter A, Jochem G (1992) Tetrahedron Lett 33:471–474
Schmidpeter A, Nöth H, Jochem G, Schrödel H-P, Karaghiosoff K (1995) Chem Ber 128:379–393
Schmidpeter A, Jochem G, Robl C, Nöth H (1997) J Organomet Chem 529:87–102
Schrödel H-P, Schmidpeter A, Nöth H (1996) Heteroat Chem 7:355–358
Jochem G, Breitsameter F, Schier A, Schmidpeter A (1996) Heteroat Chem 7:239–247
Schuhmann H, Reiher F-W (1984) J Organomet Chem 269:21–27
Rufanov KA, Müller BH, Spannenberg A, Rosenthal U (2005) New J Chem 30:29–31
Schmidbaur H, Gasser O (1976) Angew Chem Int Ed Eng 15:502–503
Smyslova EI, Perevalova EG, Dyadchenko VP, Grandberg KI, Slovokhotov YL, Struchkov YT (1981) J Organomet Chem 215:269–279
Gimeno MC, Laguna A, Laguna M, Sanmartin F, Jones PG (1993) Organometallics 12:3984–3991
Vicente J, Chicote M-T, Saura-Llamas I, Jones PG, Meyer-Bäse K, Erdbrügger CF (1988) Organometallics 7:997–1006
Vicente J, Chicote M-T, Lagunas M-C, Jones PG, Ahrens B (1997) Inorg Chem 36:4938–4944
Vicente J, Chicote M-T, Cayuelas JA, Fernandez-Baeza J, Jones PG, Sheldrick GM, Espinet P (1985) J Chem Soc Dalton Trans 1163–1168
Schmidbaur H, Schier A (2012) Chem Soc Rev 41:370–412
Vicente J, Singhal AR, Jones PG (2002) Organometallics 21:5887–5900
Schmidbaur H, Scherbaum F, Huber B, Müller G (1988) Angew Chem Int Ed Eng 27:419–421
Alcarazo M, Radkowski K, Mehler G, Goddard R, Fürstner A (2013) Chem Commun 49:3140–3142
Vicente J, Chicote MT (1999) Coord Chem Rev 193–195:1143–1161
Vicente J, Chicote MT, Lagumas M-C (1999) Helv Chim Acta 82:1202–1210
Vicente J, Chicote M-T, Guerrero R, Jones PG (1996) J Am Chem Soc 118:699–700
Sundermeyer J, Weber K, Nürnberg O (1992) J Chem Soc Chem Commun 1631–1633
Sundermeyer J, Putterlik J, Pritzkow H (1993) Chem Ber 126:289–296
Sundermeyer J, Weber K, Pritzkow H (1993) Angew Chem 105:751–753
Li X, Wang A, Wang L, Sun H, Harms K, Sundermeyer J (2007) Organometallics 27:1411–1413
Schrock RR, Hoveyda AH (2003) Angew Chem Int Ed 42:4592–4633
Li X, Schopf M, Stephan J, Harms K, Sundermeyer J (2002) Organometallics 21:2356–2358
Kreissl FR, Stueckler P (1976) J Organomet Chem 110:C9–C11
Valyaev DA, Lugan N, Lavigne G, Ustynyuk NA (2008) Organometallics 27:5180–5183
Kreissl FR, Stueckler P, Meineke EW (1977) Chem Ber 110:3040–3045
Filippou AC, Wössner D, Kociok-Köhn G, Hinz I (1997) J Organomet Chem 541:333–343
Zurawinski R, Lepetit C, Canac Y, Mikolajczyk M, Chauvin R (2009) Inorg Chem 48:2147–2155
Romero PE, Piers WE, McDonald R (2004) Angew Chem Int Ed 43:6161–6165
Romero PE, Piers WE (2005) J Am Chem Soc 127:5032–5033
Wenzel AG, Grubbs RH (2006) J Am Chem Soc 128:16048–16049
Van der Eide EF, Romero PE, Piers WE (2008) J Am Chem Soc 130:4485–4491
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Gessner, V.H. (2017). Reactivity and Applications of α-Metalated Ylides. In: Gessner, V. (eds) Modern Ylide Chemistry. Structure and Bonding, vol 177. Springer, Cham. https://doi.org/10.1007/430_2017_18
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