847:
797:
767:
918:
372:
700:
566:
789:
2098:
399:
49:
1439:, p. 85 states: "The reactivities of carbenes and carbenoids are the same no matter how they are generated." Grossman's analysis is not supported by modern physical organic chemistry texts, and likely refers to rapid equilibration between carbene states following most carbene generation methods.
913:, in which the carbene is bonded to an open-shell metal with the carbene carbon possessing a radical character. Carbene radicals have features of both Fischer and Schrock carbenes, but are typically long-lived reaction intermediates.
1560:. The transition-metal-derived carbenoids, which have a metal –– C double bond, undergo the reactions typical of singlet carbenes. At this point you can think of them as free singlet carbenes, even though they’re not."
907:, in which the carbene is bonded to a metal that bears an electron-donating group. In such cases the carbenoid carbon is nucleophilic and resembles a Wittig reagent (which are not considered carbene derivatives).
248:
It remains uncertain if these conditions form truly free carbenes or a metal-carbene complex. Nevertheless, metallocarbenes so formed give the expected organic products. In a specialized but instructive case,
781:. Insertions may or may not occur in single step (see above). The end result is that the carbene interposes itself into an existing bond, preferably X–H (X not carbon), else C–H or (failing that) a C–C bond.
317:
epoxides can potentially form two different carbenes. Typically, the C-O bond with lesser fractional bond order (fewer double-bond resonance structures) breaks. For example, when one substituent is
1344:
Grasse, P. B.; Brauer, B. E.; Zupancic, J. J.; Kaufmann, K. J.; Schuster, G. B. (1983). "Chemical and physical properties of fluorenylidene: equilibration of the singlet and triplet carbenes".
890:
MCRR' are often described as carbene complexes. Such species do not however react like free carbenes and are rarely generated from carbene precursors, except for the persistent carbenes. The
808:
produced from intramolecular insertion into a bond adjacent to the carbene center is a nuisance in some reaction schemes, as it consumes the carbene to yield the same effect as a traditional
866:. This is often, but not always, an unwanted side reaction; metal carbene dimerization has been used in the synthesis of polyalkynylethenes and is the major industrial route to Teflon (see
1835:
Nakashima, Hiroyuki; Hashimoto, Makoto; Sadakane, Yutaka; Tomohiro, Takenori; Hatanaka, Yasumaru (2006-11-01). "Simple and
Versatile Method for Tagging Phenyldiazirine Photophores".
1153:
901:, in which the carbene is bonded to a metal that bears an electron-withdrawing group (usually a carbonyl). In such cases the carbenoid carbon is mildly electrophilic.
1724:
Yang, Peng; Yang, Wantai (2013-07-10). "Surface
Chemoselective Phototransformation of C–H Bonds on Organic Polymeric Materials and Related High-Tech Applications".
2130:
3049:
816:
insertions. In flexible structures, five-membered ring formation is preferred to six-membered ring formation. When such insertions are possible, no
3054:
1548:: "Diazo compounds are converted to singlet carbenes upon gentle warming and to carbenoids by treatment with a Rh(II) or Cu(II) salt such as Rh
1107:
464:
1421:
1138:
1881:
Blencowe, Anton; Hayes, Wayne (2005-08-05). "Development and application of diazirines in biological and synthetic macromolecular systems".
785:
carbenes insert much more selectively than methylene, which does not differentiate between primary, secondary, and tertiary C-H bonds.
1708:
431:
1636:
1628:
1192:
1083:
a single carbon atom with the chemical formula :C:, in effect a twofold carbene. Also has been used to make "true carbenes" in situ.
1075:
891:
3082:
2123:
437:
364:. As with the case of metallocarbenes, some reactions of diazoalkanes that formally proceed via carbenes may instead form a
475:
mixture of singlet and triplet states with an approximately 1.1 kcal/mol (4.6 kJ/mol) energy difference, although extensive
2953:
685:. Thus methylene is a singlet carbene; if it were triplet, the product would not depend on the starting alkene geometry.
820:
insertions are seen. Both inter- and intra-molecular insertions admit asymmetric induction from a chiral metal catalyst.
616:
357:
936:
731:
214:
3087:
2526:
2116:
1059:
761:
546:
1007:
365:
2563:
1371:
Nemirowski, A.; Schreiner, P. R. (November 2007). "Electronic
Stabilization of Ground State Triplet Carbenes".
948:
883:
666:
581:
549:. Other reactions include rearrangements and dimerizations. A particular carbene's reactivity depends on the
148:
3036:
894:
can be classified according to their reactivity, with the first two classes being the most clearly defined:
813:
476:
187:
1571:
Hopkinson, M. N.; Richter, C.; Schedler, M.; Glorius, F. (2014). "An overview of N-heterocyclic carbenes".
600:
2936:
846:
202:
1411:
3043:
2931:
1261:
774:
735:
585:
530:
423:
198:
1089:
derive their stability from proximity of a double bond (i.e. their ability to form conjugated systems).
254:
3012:
2457:
2102:
1890:
1783:
1582:
940:
871:
841:
809:
608:
472:
314:
140:
52:
31:
796:
2318:
965:
361:
124:, depending upon their electronic structure. The different classes undergo different reactions.
76:
1770:
Ping, Jianfeng; Gao, Feng; Chen, Jian Lin; Webster, Richard D.; Steele, Terry W. J. (2015-08-18).
1656:
Marion, N.; Diez-Gonzalez, S.; Nolan, S. P. (2007). "N-heterocyclic carbenes as organocatalysts".
293:
Separately, carbenes can be produced from an extrusion reaction with a large free energy change.
1700:
1606:
1047:
1043:
943:
carbenes are C-deprotonated imidazolium or dihydroimidazolium salts. They often are deployed as
932:
778:
604:
518:
144:
136:
166:, two substituents eliminate from the same carbon atom. This occurs with reagents with no good
1514:
For a concise tutorial on the applications of carbene ligands also beyond diaminocarbenes, see
3077:
3002:
2972:
2730:
2352:
1987:
1952:
1914:
1906:
1860:
1852:
1817:
1799:
1749:
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1704:
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1388:
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1244:
1188:
1134:
926:
859:
805:
250:
163:
106:
60:
2707:
2201:
2139:
2076:
2049:
2018:
1979:
1944:
1898:
1844:
1807:
1791:
1733:
1696:
1665:
1640:
1590:
1573:
1527:
1458:
1380:
1353:
1277:
1269:
1236:
1167:
1039:
952:
766:
694:
468:
337:
80:
2926:
2685:
2680:
2663:
2646:
2447:
2196:
2067:
Von E. Doering, W.; Hoffmann, A. K. (1954). "The
Addition of Dichlorocarbene to Olefins".
1518:
1092:
1063:
973:
922:
910:
904:
898:
639:
620:
484:
175:
132:
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2384:
2374:
1812:
1771:
1282:
1256:
1126:
1086:
1035:
817:
635:
628:
384:
467:. However, strategies to stabilize triplet carbenes at room temperature are elusive.
3071:
3017:
2965:
2896:
2782:
2772:
2767:
2757:
2752:
2702:
2697:
2613:
2608:
2598:
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2407:
2369:
2357:
2328:
2206:
1101:
1080:
749:
739:
624:
488:
444:
171:
167:
121:
117:
1623:
S. P. Nolan "N-Heterocyclic
Carbenes in Synthesis" 2006, Wiley-VCH, Weinheim. Print
1163:
917:
447:
triplet ground state. For simple hydrocarbons, triplet carbenes are usually only 8
2948:
2835:
2830:
2807:
2558:
2397:
2323:
2260:
2255:
2233:
2189:
2174:
2164:
1226:
Bourissou, D.; Guerret, O.; Gabbai, F. P.; Bertrand, G. (2000). "Stable
Carbenes".
1051:
828:
Carbenes can form adducts with nucleophiles, and are a common precursor to various
743:
720:
708:
662:
643:
592:
577:
387:
206:
1610:
1531:
371:
1935:
Liu, Michael T. H. (1982-01-01). "The thermolysis and photolysis of diazirines".
1516:
Munz, D (2018). "Pushing
Electrons—Which Carbene Ligand for Which Application?".
3007:
2960:
2921:
2802:
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2675:
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2223:
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2184:
2179:
2169:
2147:
1407:
1158:
1023:
596:
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506:
502:
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448:
349:
302:
92:
699:
27:
Organic molecule containing a neutral carbon with two unbound valence electrons
2916:
2907:
2787:
2742:
2638:
2603:
2593:
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2392:
2340:
2022:
1228:
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829:
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646:
542:
419:
380:
329:
2053:
1991:
1956:
1910:
1856:
1803:
1745:
1569:
For a general review with a focus on applications with diaminocarbenes, see:
1162:, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "
1006:
The insertion of carbenes into C–H bonds has been exploited widely, e.g. the
127:
Most carbenes are extremely reactive and short-lived. A small number (the di
2883:
2797:
2762:
2747:
2735:
2578:
2553:
2362:
1171:
1015:
855:
712:
565:
534:
456:
427:
415:
411:
407:
294:
1918:
1864:
1821:
1753:
1677:
1669:
1602:
1392:
1291:
1273:
1248:
788:
611:. Singlet carbenes are typically electrophilic, unless they have a filled
325:, the aryl-substituted carbon is usually released as a carbene fragment.
2097:
1644:
418:
with two unpaired electrons, typically form from reactions that break two
2891:
2845:
2812:
2508:
2414:
2288:
2243:
2228:
1983:
1971:
1948:
1011:
658:
496:
353:
310:
306:
179:
68:
2080:
1594:
1462:
1357:
328:
Ring strain is not necessary for a strong thermodynamic driving force.
17:
2853:
2777:
2628:
2623:
2588:
2573:
2568:
2538:
2521:
2345:
2238:
1795:
1019:
538:
341:
298:
194:
128:
110:
42:
38:
1848:
1737:
1384:
1240:
964:
A large-scale application of carbenes is the industrial production of
870:). Persistent carbenes equilibrate with their respective dimers, the
2941:
2873:
2717:
2426:
2419:
2313:
2294:
2283:
2267:
2213:
1902:
969:
944:
863:
716:
440:) are 125–140° for triplet methylene and 102° for singlet methylene.
345:
170:
vicinal to an acidic proton are exposed to strong base; for example,
72:
2108:
2037:
2006:
1449:
Skell, P. S.; Woodworth, R. C. (1956). "Structure of
Carbene, Ch2".
398:
143:, but otherwise cannot be stored in bulk. A rare exception are the
1257:"Stable cyclic carbenes and related species beyond diaminocarbenes"
48:
2822:
2792:
2725:
2583:
2548:
2543:
2516:
2464:
2431:
2335:
2159:
916:
845:
795:
787:
782:
765:
698:
634:
The different mechanisms imply that singlet carbene additions are
564:
554:
510:
492:
460:
397:
318:
2250:
1413:
Advanced
Organic Chemistry: Reactions, Mechanisms, and Structure
480:
333:
322:
210:
30:
This article is about the chemical class. For the compound, see
2112:
1014:. Many applications rely on synthetic 3-aryl-3-trifluoromethyl
584:. Triplet carbene addition necessarily involves (at least one)
1018:(a carbene precursor that can be activated by heat, light, or
113:
from which all other carbene compounds are formally derived.
573:
Singlet and triplet carbenes exhibit divergent reactivity.
537:, but their primary synthetic utility arises from attacks on
972:. Tetrafluoroethylene is generated via the intermediacy of
253:
compounds can be isolated and separately thermolyzed. The "
615:
orbital, in which case they can react as Lewis bases. The
517:
to stabilize the singlet state. This phenomenon underlies
193:
Molecules with no acidic proton can also form carbenes. A
98:
The term "carbene" may also refer to the specific compound
1498:
1496:
1185:
The Art of
Writing Reasonable Organic Reaction Mechanisms
430:, typically form from diazo decompositions, and adopt an
422:(α elimination and some extrusion reactions), and do not
1976:
Journal of the Chemical Society, Chemical Communications
1315:
1313:
1208:
1206:
1204:
479:
into the rings complicates any conclusions drawn from di
777:
are another common type of carbene reaction, a form of
459:/mol) more stable than singlet carbenes, comparable to
159:
There are two common methods for carbene generation.
1691:
Bajzer, W. X. (2004). "Fluorine Compounds, Organic".
1255:
Melaimi, M.; Soleilhavoup, M.; Bertrand, G. (2010).
2985:
2905:
2882:
2844:
2821:
2716:
2637:
2507:
2484:
2440:
2383:
2306:
2281:
2146:
1970:Elson, Clive M.; Liu, Michael T. H. (1982-01-01).
1224:For detailed reviews on stable carbenes, see: (a)
1062:in 1954 demonstrated their synthetic utility with
436:orbital structure. Bond angles (as determined by
426:the carbene atom. Singlet carbenes have a single
2038:"Über Reaktionen des Methylens. III. Diazomethan"
951:. Such carbenes are usually very strong σ-donor
723:. Addition reactions are commonly very fast and
1772:"Adhesive curing through low-voltage activation"
1187:(2nd ed.). New York: Springer. p. 84.
1131:Molecular Orbitals of Transition Metal Complexes
727:, and carbene generation limits reaction rate.
1693:Kirk-Othmer Encyclopedia of Chemical Technology
2042:Berichte der Deutschen Chemischen Gesellschaft
2011:Berichte der Deutschen Chemischen Gesellschaft
1416:(6th ed.), New York: Wiley-Interscience,
499:carbenes, especially trifluorosilyl carbenes.
463:. The stabilization is in part attributed to
2124:
1050:also converted alkenes to cyclopropanes with
1010:of polymeric materials and electro-curing of
147:, which have extensive application in modern
8:
1701:10.1002/0471238961.0914201802011026.a01.pub2
886:species, metal complexes with the formulae L
867:
2504:
2303:
2131:
2117:
2109:
511:delocalize an electron pair into an empty
309:gas, but epoxides typically give reactive
1972:"Electrochemical behaviour of diazirines"
1811:
1281:
2069:Journal of the American Chemical Society
1837:Journal of the American Chemical Society
1545:
1502:
1487:
1475:
1451:Journal of the American Chemical Society
1436:
1346:Journal of the American Chemical Society
1331:
1319:
1304:
1212:
370:
139:) can be isolated, and can stabilize as
101:
47:
1118:
591:Singlet carbenes can (and do) react as
491:stabilize triplet carbenes, such as in
305:to carbenes. The former extrude inert
301:photolyze with a tremendous release in
1108:Ring opening metathesis polymerization
1034:Carbenes had first been postulated by
868:Carbene § Industrial applications
368:intermediate that extrudes nitrogen.
1930:
1928:
1876:
1874:
1765:
1763:
812:. Generally, rigid structures favor
707:Carbenes add to double bonds to form
529:Carbenes behave like very aggressive
505:nitrogen, oxygen, sulphur, or halide
186:). Such reactions typically require
7:
483:carbenes. Simulations suggest that
213:abstracts halogens similarly in the
2036:Staudinger, H.; Kupfer, O. (1912).
878:Ligands in organometallic chemistry
711:, and, in the presence of a copper
541:, which give cyclopropanes; and on
465:Hund's rule of maximum multiplicity
383:carbene a ketone can be exposed to
2005:Buchner, E.; Feldmann, L. (1903).
1159:Compendium of Chemical Terminology
1076:Transition metal carbene complexes
892:transition metal carbene complexes
509:bonded to the divalent carbon can
25:
1183:Grossman, Robert B. (2003).
1022:) but there is a whole family of
603:. Their reactions are typically
116:There are two types of carbenes:
2096:
414:carbenes. Triplet carbenes are
406:The two classes of carbenes are
921:The "second generation" of the
800:Carbene intermolecular reaction
792:Carbene intramolecular reaction
588:with two unpaired electrons.
471:has been shown to be a rapidly
732:Simmons-Smith cyclopropanation
638:but triplet carbene additions
580:, and participate in stepwise
1:
1532:10.1021/acs.organomet.7b00720
2007:"Diazoessigester und Toluol"
402:Singlet and triplet carbenes
738:typically complexes to any
569:Carbene addition to alkenes
3104:
839:
759:
692:
521:' remarkable stability.
36:
29:
3026:
2023:10.1002/cber.190303603139
1695:. John Wiley & Sons.
352:to a carbene and gaseous
188:phase-transfer conditions
83:. The general formula is
2054:10.1002/cber.19120450174
1937:Chemical Society Reviews
955:, similar to phosphines.
949:organometallic chemistry
703:Carbene cyclopropanation
667:1,2-dimethylcyclopropane
617:Bamford–Stevens reaction
390:and then a strong base.
358:Bamford–Stevens reaction
149:organometallic chemistry
79:of two and two unshared
55:is the simplest carbene.
37:Not to be confused with
3037:chemical classification
1172:10.1351/goldbook.C00806
960:Industrial applications
929:features an NHC ligand.
561:Singlet-triplet effects
477:electron delocalization
209:to give a carbene, and
91:where the R represents
3083:Reactive intermediates
1670:10.1002/anie.200603380
1274:10.1002/anie.201000165
1046:with toluene. In 1912
930:
851:
801:
793:
771:
742:such that addition is
740:allylic hydroxy groups
704:
570:
403:
394:Structures and bonding
376:
215:Simmons–Smith reaction
203:metal-halogen exchange
56:
3044:chemical nomenclature
1776:Nature Communications
1645:10.1002/9783527609451
1262:Angew. Chem. Int. Ed.
1133:. Oxford. p. 7.
1104:, protonated carbenes
920:
849:
799:
791:
769:
762:Carbene C−H insertion
736:iodomethylzinc iodide
702:
576:Triplet carbenes are
568:
443:Most carbenes have a
401:
374:
356:; this occurs in the
340:catalysts (typically
205:and then eliminate a
71:containing a neutral
51:
2105:at Wikimedia Commons
1984:10.1039/c39820000415
1949:10.1039/cs9821100127
1658:Angew. Chem. Int. Ed
1058:as an intermediate.
872:Wanzlick equilibrium
850:Wanzlick equilibrium
842:Carbene dimerization
836:Carbene dimerization
824:Electrophilic attack
810:elimination reaction
197:dihalide exposed to
32:Methylene (compound)
2500:not C, H or O)
2081:10.1021/ja01652a087
1895:2005SMat....1..178B
1843:(47): 15092–15093.
1788:2015NatCo...6.8050P
1595:10.1038/nature13384
1587:2014Natur.510..485H
1463:10.1021/ja01598a087
1406:Smith, Michael B.;
1358:10.1021/ja00361a014
968:, the precursor to
966:tetrafluoroethylene
649:reacts with either
533:. They can attack
519:persistent carbenes
362:Wolff rearrangement
145:persistent carbenes
95:or hydrogen atoms.
2942:Hypervalent iodine
1796:10.1038/ncomms9050
1048:Hermann Staudinger
1044:ethyl diazoacetate
931:
852:
802:
794:
779:oxidative addition
772:
705:
619:gives carbenes in
571:
461:nitrogen inversion
404:
377:
375:Alkylidene carbene
137:carbon monosulfide
57:
3088:Functional groups
3065:
3064:
3003:Sulfenyl chloride
2981:
2980:
2480:
2479:
2299:(only C, H and O)
2140:Functional groups
2101:Media related to
1849:10.1021/ja066479y
1738:10.1021/cr300246p
1664:(17): 2988–3000.
1581:(7506): 485–496.
1490:, pp. 86–87.
1478:, pp. 85–86.
1423:978-0-471-72091-1
1385:10.1021/jo701615x
1379:(25): 9533–9540.
1307:, pp. 84–85.
1268:(47): 8810–8849.
1241:10.1021/cr940472u
1140:978-0-19-853093-0
1008:functionalization
953:spectator ligands
945:ancillary ligands
927:alkene metathesis
806:1,2-rearrangement
770:Carbene insertion
661:to give a single
642:. Methylene from
582:radical additions
547:carbene insertion
489:thermodynamically
81:valence electrons
61:organic chemistry
16:(Redirected from
3095:
3032:
2937:Trifluoromethoxy
2505:
2501:
2304:
2300:
2153:
2133:
2126:
2119:
2110:
2100:
2085:
2084:
2064:
2058:
2057:
2033:
2027:
2026:
2002:
1996:
1995:
1967:
1961:
1960:
1932:
1923:
1922:
1903:10.1039/b501989c
1878:
1869:
1868:
1832:
1826:
1825:
1815:
1767:
1758:
1757:
1732:(7): 5547–5594.
1726:Chemical Reviews
1721:
1715:
1714:
1688:
1682:
1681:
1653:
1647:
1621:
1615:
1614:
1567:
1561:
1542:
1536:
1535:
1512:
1506:
1500:
1491:
1485:
1479:
1473:
1467:
1466:
1446:
1440:
1433:
1427:
1426:
1403:
1397:
1396:
1368:
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1361:
1341:
1335:
1329:
1323:
1317:
1308:
1302:
1296:
1295:
1285:
1252:
1222:
1216:
1210:
1199:
1198:
1180:
1174:
1151:
1145:
1144:
1123:
1040:cyclopropanation
923:Grubbs catalysts
911:Carbene radicals
905:Schrock carbenes
899:Fischer carbenes
695:Cyclopropanation
689:Cyclopropanation
621:aprotic solvents
553:, including any
487:heteroatoms can
469:9-Fluorenylidene
338:transition metal
255:Seyferth reagent
233:CLi(Br) + BuBr
104:
90:
86:
21:
3103:
3102:
3098:
3097:
3096:
3094:
3093:
3092:
3068:
3067:
3066:
3061:
3030:
3022:
2977:
2932:Trichloromethyl
2927:Trifluoromethyl
2901:
2878:
2840:
2817:
2712:
2681:Phosphine oxide
2633:
2499:
2497:
2496:
2494:
2492:
2490:
2488:
2486:
2476:
2436:
2379:
2298:
2297:
2292:
2287:
2277:
2151:
2150:
2142:
2137:
2093:
2088:
2066:
2065:
2061:
2035:
2034:
2030:
2004:
2003:
1999:
1969:
1968:
1964:
1934:
1933:
1926:
1880:
1879:
1872:
1834:
1833:
1829:
1769:
1768:
1761:
1723:
1722:
1718:
1711:
1690:
1689:
1685:
1655:
1654:
1650:
1622:
1618:
1570:
1568:
1564:
1559:
1555:
1551:
1543:
1539:
1519:Organometallics
1515:
1513:
1509:
1501:
1494:
1486:
1482:
1474:
1470:
1448:
1447:
1443:
1434:
1430:
1424:
1405:
1404:
1400:
1370:
1369:
1365:
1343:
1342:
1338:
1330:
1326:
1318:
1311:
1303:
1299:
1254:
1225:
1223:
1219:
1211:
1202:
1195:
1182:
1181:
1177:
1152:
1148:
1141:
1127:Hoffmann, Roald
1125:
1124:
1120:
1116:
1093:Carbene analogs
1087:Foiled carbenes
1072:
1064:dichlorocarbene
1057:
1032:
1002:
998:
994:
987:
983:
974:difluorocarbene
962:
889:
880:
858:precursors can
844:
838:
826:
764:
758:
697:
691:
640:stereoselective
563:
527:
485:electropositive
396:
379:To generate an
288:
284:
280:
276:
272:
268:
260:
243:
239:
232:
228:
224:
185:
157:
133:carbon monoxide
103:
99:
88:
84:
46:
35:
28:
23:
22:
15:
12:
11:
5:
3101:
3099:
3091:
3090:
3085:
3080:
3070:
3069:
3063:
3062:
3060:
3059:
3058:
3057:
3052:
3040:
3033:
3027:
3024:
3023:
3021:
3020:
3018:Sulfinylamines
3015:
3010:
3005:
3000:
2998:Phosphoramides
2995:
2993:Isothiocyanate
2989:
2987:
2983:
2982:
2979:
2978:
2976:
2975:
2970:
2969:
2968:
2958:
2957:
2956:
2946:
2945:
2944:
2939:
2934:
2929:
2924:
2913:
2911:
2903:
2902:
2900:
2899:
2894:
2888:
2886:
2880:
2879:
2877:
2876:
2871:
2869:Selenenic acid
2866:
2864:Seleninic acid
2861:
2859:Selenonic acid
2856:
2850:
2848:
2842:
2841:
2839:
2838:
2833:
2827:
2825:
2819:
2818:
2816:
2815:
2810:
2805:
2800:
2795:
2790:
2785:
2780:
2775:
2770:
2765:
2760:
2755:
2750:
2745:
2740:
2739:
2738:
2728:
2722:
2720:
2714:
2713:
2711:
2710:
2705:
2700:
2695:
2694:
2693:
2683:
2678:
2673:
2668:
2667:
2666:
2656:
2655:
2654:
2652:Phosphodiester
2643:
2641:
2635:
2634:
2632:
2631:
2626:
2621:
2616:
2611:
2606:
2601:
2596:
2591:
2586:
2581:
2576:
2571:
2566:
2561:
2556:
2551:
2546:
2541:
2536:
2531:
2530:
2529:
2524:
2513:
2511:
2502:
2498:(one element,
2482:
2481:
2478:
2477:
2475:
2474:
2473:
2472:
2462:
2461:
2460:
2455:
2444:
2442:
2438:
2437:
2435:
2434:
2429:
2424:
2423:
2422:
2412:
2411:
2410:
2405:
2400:
2389:
2387:
2381:
2380:
2378:
2377:
2375:Methylenedioxy
2372:
2367:
2366:
2365:
2360:
2350:
2349:
2348:
2343:
2333:
2332:
2331:
2321:
2316:
2310:
2308:
2301:
2279:
2278:
2276:
2275:
2270:
2265:
2264:
2263:
2258:
2248:
2247:
2246:
2241:
2236:
2231:
2226:
2221:
2211:
2210:
2209:
2204:
2194:
2193:
2192:
2187:
2182:
2177:
2172:
2167:
2156:
2154:
2152:(only C and H)
2144:
2143:
2138:
2136:
2135:
2128:
2121:
2113:
2107:
2106:
2092:
2091:External links
2089:
2087:
2086:
2059:
2028:
1997:
1978:(7): 415–416.
1962:
1924:
1889:(3): 178–205.
1870:
1827:
1759:
1716:
1710:978-0471238966
1709:
1683:
1648:
1616:
1562:
1557:
1553:
1549:
1544:Contrariwise,
1537:
1526:(3): 275–289.
1507:
1492:
1480:
1468:
1441:
1435:Contrariwise,
1428:
1422:
1398:
1363:
1336:
1324:
1309:
1297:
1217:
1200:
1193:
1175:
1146:
1139:
1117:
1115:
1112:
1111:
1110:
1105:
1102:Carbenium ions
1099:
1090:
1084:
1078:
1071:
1068:
1055:
1036:Eduard Buchner
1031:
1028:
1004:
1003:
1000:
996:
992:
989:
985:
981:
961:
958:
957:
956:
933:N-Heterocyclic
914:
908:
902:
887:
884:organometallic
879:
876:
840:Main article:
837:
834:
825:
822:
818:intermolecular
814:intramolecular
760:Main article:
757:
754:
693:Main article:
690:
687:
636:stereospecific
625:carbenium ions
562:
559:
545:, which cause
526:
523:
395:
392:
385:trimethylsilyl
291:
290:
286:
282:
278:
274:
270:
266:
261:upon heating:
258:
257:" releases CCl
246:
245:
241:
237:
234:
230:
226:
222:
199:organolithiums
183:
174:will abstract
168:leaving groups
156:
153:
105:, also called
26:
24:
14:
13:
10:
9:
6:
4:
3:
2:
3100:
3089:
3086:
3084:
3081:
3079:
3076:
3075:
3073:
3056:
3053:
3051:
3048:
3047:
3046:
3045:
3041:
3039:
3038:
3034:
3029:
3028:
3025:
3019:
3016:
3014:
3011:
3009:
3006:
3004:
3001:
2999:
2996:
2994:
2991:
2990:
2988:
2984:
2974:
2971:
2967:
2964:
2963:
2962:
2959:
2955:
2952:
2951:
2950:
2947:
2943:
2940:
2938:
2935:
2933:
2930:
2928:
2925:
2923:
2920:
2919:
2918:
2915:
2914:
2912:
2910:
2909:
2904:
2898:
2897:Telluroketone
2895:
2893:
2890:
2889:
2887:
2885:
2881:
2875:
2872:
2870:
2867:
2865:
2862:
2860:
2857:
2855:
2852:
2851:
2849:
2847:
2843:
2837:
2834:
2832:
2829:
2828:
2826:
2824:
2820:
2814:
2811:
2809:
2806:
2804:
2801:
2799:
2796:
2794:
2791:
2789:
2786:
2784:
2783:Sulfonic acid
2781:
2779:
2776:
2774:
2773:Sulfinic acid
2771:
2769:
2768:Thiosulfonate
2766:
2764:
2761:
2759:
2758:Thiosulfinate
2756:
2754:
2753:Sulfenic acid
2751:
2749:
2746:
2744:
2741:
2737:
2734:
2733:
2732:
2729:
2727:
2724:
2723:
2721:
2719:
2715:
2709:
2708:Phosphaallene
2706:
2704:
2703:Phosphaalkyne
2701:
2699:
2698:Phosphaalkene
2696:
2692:
2689:
2688:
2687:
2684:
2682:
2679:
2677:
2674:
2672:
2669:
2665:
2662:
2661:
2660:
2657:
2653:
2650:
2649:
2648:
2645:
2644:
2642:
2640:
2636:
2630:
2627:
2625:
2622:
2620:
2617:
2615:
2612:
2610:
2607:
2605:
2602:
2600:
2597:
2595:
2592:
2590:
2587:
2585:
2582:
2580:
2577:
2575:
2572:
2570:
2567:
2565:
2562:
2560:
2557:
2555:
2552:
2550:
2547:
2545:
2542:
2540:
2537:
2535:
2532:
2528:
2525:
2523:
2520:
2519:
2518:
2515:
2514:
2512:
2510:
2506:
2503:
2483:
2471:
2468:
2467:
2466:
2463:
2459:
2456:
2454:
2451:
2450:
2449:
2446:
2445:
2443:
2439:
2433:
2430:
2428:
2425:
2421:
2418:
2417:
2416:
2413:
2409:
2406:
2404:
2401:
2399:
2396:
2395:
2394:
2391:
2390:
2388:
2386:
2382:
2376:
2373:
2371:
2370:Ethylenedioxy
2368:
2364:
2361:
2359:
2356:
2355:
2354:
2351:
2347:
2344:
2342:
2339:
2338:
2337:
2334:
2330:
2327:
2326:
2325:
2322:
2320:
2317:
2315:
2312:
2311:
2309:
2305:
2302:
2296:
2290:
2285:
2280:
2274:
2271:
2269:
2266:
2262:
2259:
2257:
2254:
2253:
2252:
2249:
2245:
2242:
2240:
2237:
2235:
2232:
2230:
2227:
2225:
2222:
2220:
2217:
2216:
2215:
2212:
2208:
2205:
2203:
2200:
2199:
2198:
2195:
2191:
2188:
2186:
2183:
2181:
2178:
2176:
2173:
2171:
2168:
2166:
2163:
2162:
2161:
2158:
2157:
2155:
2149:
2145:
2141:
2134:
2129:
2127:
2122:
2120:
2115:
2114:
2111:
2104:
2099:
2095:
2094:
2090:
2082:
2078:
2074:
2070:
2063:
2060:
2055:
2051:
2047:
2043:
2039:
2032:
2029:
2024:
2020:
2016:
2012:
2008:
2001:
1998:
1993:
1989:
1985:
1981:
1977:
1973:
1966:
1963:
1958:
1954:
1950:
1946:
1942:
1938:
1931:
1929:
1925:
1920:
1916:
1912:
1908:
1904:
1900:
1896:
1892:
1888:
1884:
1877:
1875:
1871:
1866:
1862:
1858:
1854:
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1814:
1809:
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1801:
1797:
1793:
1789:
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1773:
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1760:
1755:
1751:
1747:
1743:
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1727:
1720:
1717:
1712:
1706:
1702:
1698:
1694:
1687:
1684:
1679:
1675:
1671:
1667:
1663:
1659:
1652:
1649:
1646:
1642:
1638:
1637:9783527609451
1634:
1630:
1629:9783527314003
1626:
1620:
1617:
1612:
1608:
1604:
1600:
1596:
1592:
1588:
1584:
1580:
1576:
1575:
1566:
1563:
1547:
1546:Grossman 2003
1541:
1538:
1533:
1529:
1525:
1521:
1520:
1511:
1508:
1505:, p. 87.
1504:
1503:Grossman 2003
1499:
1497:
1493:
1489:
1488:Grossman 2003
1484:
1481:
1477:
1476:Grossman 2003
1472:
1469:
1464:
1460:
1456:
1452:
1445:
1442:
1438:
1437:Grossman 2003
1432:
1429:
1425:
1419:
1415:
1414:
1409:
1402:
1399:
1394:
1390:
1386:
1382:
1378:
1374:
1367:
1364:
1359:
1355:
1351:
1347:
1340:
1337:
1334:, p. 84.
1333:
1332:Grossman 2003
1328:
1325:
1322:, p. 85.
1321:
1320:Grossman 2003
1316:
1314:
1310:
1306:
1305:Grossman 2003
1301:
1298:
1293:
1289:
1284:
1279:
1275:
1271:
1267:
1264:
1263:
1258:
1250:
1246:
1242:
1238:
1234:
1231:
1230:
1221:
1218:
1215:, p. 35.
1214:
1213:Grossman 2003
1209:
1207:
1205:
1201:
1196:
1194:0-387-95468-6
1190:
1186:
1179:
1176:
1173:
1169:
1165:
1161:
1160:
1155:
1150:
1147:
1142:
1136:
1132:
1128:
1122:
1119:
1113:
1109:
1106:
1103:
1100:
1098:
1094:
1091:
1088:
1085:
1082:
1081:Atomic carbon
1079:
1077:
1074:
1073:
1069:
1067:
1065:
1061:
1053:
1049:
1045:
1041:
1037:
1029:
1027:
1025:
1021:
1017:
1013:
1009:
990:
979:
978:
977:
975:
971:
967:
959:
954:
950:
946:
942:
938:
934:
928:
924:
919:
915:
912:
909:
906:
903:
900:
897:
896:
895:
893:
885:
877:
875:
873:
869:
865:
861:
857:
854:Carbenes and
848:
843:
835:
833:
831:
823:
821:
819:
815:
811:
807:
798:
790:
786:
784:
780:
776:
768:
763:
756:C—H insertion
755:
753:
751:
750:hydroxy group
747:
746:
741:
737:
733:
728:
726:
722:
721:cyclopropenes
718:
714:
710:
709:cyclopropanes
701:
696:
688:
686:
684:
680:
676:
672:
668:
664:
660:
656:
652:
648:
645:
641:
637:
632:
630:
626:
622:
618:
614:
610:
606:
602:
598:
594:
593:electrophiles
589:
587:
583:
579:
574:
567:
560:
558:
556:
552:
548:
544:
540:
536:
532:
524:
522:
520:
516:
514:
508:
504:
500:
498:
494:
490:
486:
482:
478:
474:
473:equilibrating
470:
466:
462:
458:
454:
450:
446:
441:
439:
435:
434:
429:
425:
421:
417:
413:
409:
400:
393:
391:
389:
386:
382:
373:
369:
367:
363:
359:
355:
351:
347:
343:
339:
335:
331:
326:
324:
320:
316:
312:
308:
304:
300:
296:
264:
263:
262:
256:
252:
240:CLi(Br) → R
235:
229:+ BuLi → R
220:
219:
218:
216:
212:
208:
204:
200:
196:
191:
189:
181:
177:
173:
172:phenyllithium
169:
165:
164:α elimination
160:
154:
152:
150:
146:
142:
141:metal ligands
138:
134:
130:
125:
123:
119:
114:
112:
109:, the parent
108:
96:
94:
82:
78:
74:
70:
66:
62:
54:
50:
44:
40:
33:
19:
3042:
3035:
2949:Vinyl halide
2906:
2836:Borinic acid
2831:Boronic acid
2808:Thioxanthate
2272:
2148:Hydrocarbons
2075:(23): 6162.
2072:
2068:
2062:
2045:
2041:
2031:
2014:
2010:
2000:
1975:
1965:
1940:
1936:
1886:
1882:
1840:
1836:
1830:
1779:
1775:
1729:
1725:
1719:
1692:
1686:
1661:
1657:
1651:
1619:
1578:
1572:
1565:
1540:
1523:
1517:
1510:
1483:
1471:
1457:(17): 4496.
1454:
1450:
1444:
1431:
1412:
1408:March, Jerry
1401:
1376:
1373:J. Org. Chem
1372:
1366:
1352:(23): 6833.
1349:
1345:
1339:
1327:
1300:
1265:
1260:
1235:(1): 39–91.
1232:
1227:
1220:
1184:
1178:
1157:
1149:
1130:
1121:
1052:diazomethane
1033:
1024:carbene dyes
1005:
963:
881:
853:
827:
803:
773:
744:
729:
706:
682:
678:
674:
670:
663:diastereomer
654:
650:
644:diazomethane
633:
612:
597:nucleophiles
590:
586:intermediate
575:
572:
551:substituents
528:
512:
507:substituents
501:
442:
432:
405:
388:diazomethane
378:
350:diazoalkanes
348:) decompose
327:
321:and another
313:wastes, and
292:
247:
207:lithium salt
201:can undergo
192:
161:
158:
126:
115:
97:
93:substituents
75:atom with a
64:
58:
3013:Thiocyanate
3008:Sulfonamide
2973:Perchlorate
2961:Acyl halide
2922:Fluoroethyl
2803:Thionoester
2691:Phosphonium
2676:Phosphinate
2671:Phosphonous
2659:Phosphonate
2358:Hydroperoxy
2180:Cyclopropyl
2048:: 501–509.
2017:(3): 3509.
1883:Soft Matter
1042:studies of
1038:in 1903 in
830:1,3-dipoles
629:protic ones
609:cheletropic
531:Lewis acids
503:Lewis-basic
424:rehybridize
366:cycloadduct
303:ring strain
3072:Categories
2917:Haloalkane
2788:Thioketone
2743:Persulfide
2639:Phosphorus
2604:Isocyanate
2594:Isonitrile
2495:or oxygen
2493:hydrogen,
2489:not being
2470:Orthoester
2363:Dioxiranes
2341:Enol ether
2229:1-Propenyl
1943:(2): 127.
1229:Chem. Rev.
1114:References
1097:carbenoids
1016:diazirines
775:Insertions
725:exothermic
647:photolysis
607:and often
601:ambiphiles
578:diradicals
557:present.
535:lone pairs
525:Reactivity
416:diradicals
381:alkylidene
330:Photolysis
315:asymmetric
295:Diazirines
244:C + LiBr
211:zinc metal
155:Generation
131:carbenes,
3050:inorganic
2884:Tellurium
2798:Thioester
2763:Sulfoxide
2748:Disulfide
2736:Sulfonium
2686:Phosphine
2664:Phosphite
2647:Phosphate
2579:Carbamate
2554:Hydrazone
2487:element,
2485:Only one
2458:Anhydride
2197:Methylene
1992:0022-4936
1957:1460-4744
1911:1744-6848
1857:0002-7863
1804:2041-1723
1746:0009-2665
1631:. Online
1012:adhesives
856:carbenoid
605:concerted
445:nonlinear
428:lone pair
107:methylene
53:Methylene
3078:Carbenes
3031:See also
2966:Chloride
2892:Tellurol
2846:Selenium
2813:Xanthate
2527:Ammonium
2509:Nitrogen
2491:carbon,
2448:Carboxyl
2415:Aldehyde
2403:Acryloyl
2385:carbonyl
2289:hydrogen
2244:Cumulene
2103:Carbenes
1919:32646075
1865:17117852
1822:26282730
1782:: 8050.
1754:23614481
1678:17348057
1603:24965649
1410:(2007),
1393:17994760
1292:20836099
1249:11749234
1164:carbenes
1129:(2005).
1070:See also
941:Wanzlick
937:Arduengo
860:dimerize
719:to give
713:catalyst
659:2-butene
497:silyloxy
354:nitrogen
311:carbonyl
307:nitrogen
299:epoxides
180:haloform
122:triplets
118:singlets
69:molecule
18:Carbenes
3055:organic
2854:Selenol
2778:Sulfone
2731:Sulfide
2629:NONOate
2624:Nitroso
2614:Nitrite
2609:Nitrate
2599:Cyanate
2589:Nitrile
2574:Amidine
2569:Imidate
2539:Nitrene
2534:Hydrazo
2522:Enamine
2453:Acetoxy
2441:carboxy
2408:Benzoyl
2346:Epoxide
2329:Methoxy
2319:Alcohol
2273:Carbene
2207:Methine
1891:Bibcode
1813:4557340
1784:Bibcode
1583:Bibcode
1556:or CuCl
1283:3130005
1060:Doering
1030:History
1020:voltage
935:(NHC),
864:alkenes
748:to the
717:alkynes
543:σ bonds
539:π bonds
515:orbital
420:σ bonds
412:triplet
408:singlet
342:rhodium
251:mercury
195:geminal
178:from a
111:hydride
85:R−:C−R'
77:valence
65:carbene
43:carbyne
39:carbine
2954:Iodide
2874:Selone
2718:Sulfur
2427:Ketone
2420:Ketene
2398:Acetyl
2353:Peroxy
2324:Alkoxy
2314:Acetal
2295:oxygen
2284:carbon
2268:Alkyne
2261:Benzyl
2256:Phenyl
2239:Allene
2234:Crotyl
2214:Alkene
2202:Bridge
2190:Pentyl
2175:Propyl
2165:Methyl
1990:
1955:
1917:
1909:
1863:
1855:
1820:
1810:
1802:
1752:
1744:
1707:
1676:
1635:
1627:
1611:672379
1609:
1601:
1574:Nature
1420:
1391:
1290:
1280:
1247:
1191:
1137:
1054:and CH
988:+ HCl
984:→ CF
970:Teflon
734:, the
555:metals
346:copper
277:→ CCl
249:α-halo
135:, and
73:carbon
2986:Other
2823:Boron
2793:Thial
2726:Thiol
2619:Nitro
2584:Imide
2564:Amide
2549:Oxime
2544:Imine
2517:Amine
2465:Ester
2432:Ynone
2336:Ether
2307:R-O-R
2282:Only
2224:Allyl
2219:Vinyl
2185:Butyl
2170:Ethyl
2160:Alkyl
1607:S2CID
1552:(OAc)
1154:IUPAC
995:→ F
980:CHClF
783:Alkyl
715:, to
683:trans
681:from
679:trans
673:from
655:trans
653:- or
599:, or
493:silyl
336:, or
319:alkyl
273:HgCCl
67:is a
2908:Halo
2393:Acyl
2293:and
2251:Aryl
1988:ISSN
1953:ISSN
1915:PMID
1907:ISSN
1861:PMID
1853:ISSN
1818:PMID
1800:ISSN
1750:PMID
1742:ISSN
1705:ISBN
1674:PMID
1633:ISBN
1625:ISBN
1599:PMID
1418:ISBN
1389:PMID
1288:PMID
1253:(b)
1245:PMID
1189:ISBN
1135:ISBN
1095:and
1026:.
999:C=CF
991:2 CF
925:for
832:.
804:The
677:and
623:and
495:and
481:aryl
455:(33
449:kcal
410:and
360:and
344:and
334:heat
323:aryl
297:and
289:HgCl
281:+ C
217:.
190:.
182:(CHX
151:.
129:halo
89:R=C:
63:, a
2559:Azo
2077:doi
2050:doi
2019:doi
1980:doi
1945:doi
1899:doi
1845:doi
1841:128
1808:PMC
1792:doi
1734:doi
1730:113
1697:doi
1666:doi
1641:doi
1591:doi
1579:510
1528:doi
1459:doi
1381:doi
1354:doi
1350:105
1278:PMC
1270:doi
1237:doi
1233:100
1168:doi
1166:".
947:in
939:or
882:In
862:to
745:syn
730:In
675:cis
671:cis
665:of
651:cis
627:in
453:mol
438:EPR
225:CBr
162:In
120:or
100::CH
87:or
59:In
41:or
3074::
2291:,
2286:,
2073:76
2071:.
2046:45
2044:.
2040:.
2015:36
2013:.
2009:.
1986:.
1974:.
1951:.
1941:11
1939:.
1927:^
1913:.
1905:.
1897:.
1885:.
1873:^
1859:.
1851:.
1839:.
1816:.
1806:.
1798:.
1790:.
1778:.
1774:.
1762:^
1748:.
1740:.
1728:.
1703:.
1672:.
1662:46
1660:.
1639:.
1605:.
1597:.
1589:.
1577:.
1524:37
1522:.
1495:^
1455:78
1453:.
1387:.
1377:72
1375:.
1348:.
1312:^
1286:.
1276:.
1266:49
1259:.
1243:.
1203:^
1156:,
1066:.
976::
874:.
752:.
669::
631:.
595:,
457:kJ
433:sp
332:,
176:HX
2132:e
2125:t
2118:v
2083:.
2079::
2056:.
2052::
2025:.
2021::
1994:.
1982::
1959:.
1947::
1921:.
1901::
1893::
1887:1
1867:.
1847::
1824:.
1794::
1786::
1780:6
1756:.
1736::
1713:.
1699::
1680:.
1668::
1643::
1613:.
1593::
1585::
1558:2
1554:4
1550:2
1534:.
1530::
1465:.
1461::
1395:.
1383::
1360:.
1356::
1294:.
1272::
1251:.
1239::
1197:.
1170::
1143:.
1056:2
1001:2
997:2
993:2
986:2
982:2
888:n
657:-
613:p
513:p
451:/
287:5
285:H
283:6
279:2
275:3
271:5
269:H
267:6
265:C
259:2
242:2
238:2
236:R
231:2
227:2
223:2
221:R
184:3
102:2
45:.
34:.
20:)
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