参考文献
[1]Bertrand G.Carbene chemistry：From fleeting intermediates to powerful reagents[M].New York：Marcel Dekker，Inc.，2002.
[2]Fischer E O，Maasböl A.On the existence of a tungsten carbonyl carbene complex[J].Angewandte Chemie International Edition in English，1964，3（8）：580-581.
[3]Guggenberger L J，Schrock R R.Structure of bis （cyclopentadienyl）methylmethylenetantalum and the estimated barrier to rotation about the tantalum-methylene bond[J].Journal of the American Chemical Society，1975，97（22）：6578-6579.
[4]Hopkinson M N，Richter C，Schedler M，et al.An overview of N-heterocyclic carbenes[J].Nature，2014，510（7506）：485-496.
[5]Trnka T M，Grubbs R H.The development of L2X2Ru═CHR olefin metathesis catalysts：An organometallic success story[J].Accounts of Chemical Research，2001，34（1）：18-29.
[6]Peloso R，Carmona E.Non-heteroatom-substituted alkylidene complexes of groups 10 and 11[J].Coordination Chemistry Reviews，2018，355：116-132.
[7]Mindiola D J，Hillhouse G L.Synthesis，structure，and reactions of a three-coordinate nickel-carbene complex，{1，2-bis （di-tert-butylphosphino）ethane}Ni═CPh2[J].Journal of the American Chemical Society，2002，124（34）：9976-9977.
[8]Bröring M，Brandt C D，Stellwag S.The first PdⅡ complex of a non-heteroatom stabilised carbene ligand[J].Chemical Communications，2003（18）：2344-2345.
[9]Seidel G，Fürstner A.Structure of a reactive gold carbenoid[J].Angewandte Chemie International Edition，2014，53（19）：4807-4811.
[10]Harris R J，Widenhoefer R A.Synthesis，structure，and reactivity of a gold carbenoid complex that lacks heteroatom stabilization[J].Angewandte Chemie International Edition，2014，53（35）：9369-9371.
[11]Zeineddine A，Rekhroukh F，Carrizo E D S，et al.Isolation of a reactive tricoordinate α-oxo gold carbene complex[J].Angewandte Chemie International Edition，2018，57（5）：1306-1310.
[12]Hussong M W，Hoffmeister W T，Rominger F，et al.Copper and silver carbene complexes without heteroatom-stabilization：Structure，spectroscopy，and relativistic effects[J].Angewandte Chemie International Edition，2015，54（35）：10331-10335.
[13]Tskhovrebov A G，Goddard R，Fürstner A.Two amphoteric silver carbene clusters[J].Angewandte Chemie International Edition，2018，57（27）：8089-8094.
[14]Kornecki K P，Briones J F，Boyarskikh V，et al.Direct spectroscopic characterization of a transitory dirhodium donor-acceptor carbene complex[J].Science，2013，342（6156）：351-354.
[15]Werlé C，Goddard R，Fürstner A.The first crystal structure of a reactive dirhodium carbene complex and a versatile method for the preparation of gold carbenes by rhodium-to-gold transmetalation[J].Angewandte Chemie International Edition，2015，54（51）：15452-15456.
[16]Werlé C，Goddard R，Philipps P，et al.Stabilization of a chiral dirhodium carbene by encapsulation and a discussion of the stereochemical implications[J].Angewandte Chemie International Edition，2016，55（36）：10760-10765.
[17]Werlé C，Goddard R，Philipps P，et al.Structures of reactive donor/acceptor and donor/donor rhodium carbenes in the solid state and their implications for catalysis[J].Journal of the American Chemical Society，2016，138（11）：3797-3805.
[18]Kirmse W，Kapps M.Reaktionen des diazomethans mit diallylsulfid und allyläthern unter kupfersalz-katalyse[J].Chemische Berichte，1968，101（3）：994-1003.
[19]Doyle M P，Tamblyn W H，Bagheri V.Highly effective catalytic methods for ylide generation from diazo compounds.Mechanism of the rhodium-and copper-catalyzed reactions with allylic compounds[J].The Journal of Organic Chemistry，1981，46（25）：5094-5102.
[20]Nishibayashi Y，Ohe K，Uemura S.The first example of enantioselective carbenoid addition to organochalcogen atoms：Application to [2，3]sigmatropic rearrangement of allylic chalcogen ylides[J].Journal of the Chemical Society，Chemical Communications，1995（12）：1245-1246.
[21]Ma M，Peng L L，Li C K，et al.Highly stereoselective [2，3]-sigmatropic rearrangement of sulfur ylide generated through Cu（Ⅰ）carbene and sulfides[J].Journal of the American Chemical Society，2005，127（43）：15016-15017.
[22]Zhang Z K，Sheng Z，Yu W Z，et al.Catalytic asymmetric trifluoromethylthiolation viaenantioselective [2，3]-sigmatropic rearrangement of sulfonium ylides[J].Nature Chemistry，2017，9（10）：970-976.
[23]Pirrung M C，Werner J A.Intramolecular generation and [2，3]-sigmatropic rearrangement of oxonium ylides[J].Journal of the American Chemical Society，1986，108（19）：6060-6062.
[24]Roskamp E J，Johnson C R.Generation and rearrangements of oxonium ylides[J].Journal of the American Chemical Society，1986，108（19）：6062-6063.
[25]Roberts E，Sançon J P，Sweeney J B，et al.First efficient and general copper-catalyzed [2，3]-rearrangement of tetrahydropyridinium ylids[J].Organic Letters，2003，5（25）：4775-4777.
[26]Vanecko J A，Wan H，West F G.Recent advances in the Stevens rearrangement of ammonium ylides.Application to the synthesis of alkaloid natural products[J].Tetrahedron，2006，62（6）：1043-1062.
[27]Padwa A，Weingarten M D.Cascade processes of metallo carbenoids[J].Chemical Reviews，1996，96（1）：223-270.
[28]Padwa A.Intramolecular cycloaddition of carbonyl ylides as a strategy for natural product synthesis[J].Tetrahedron，2011，67（42）：8057-8072.
[29]Zhu S F，Zhou Q L.Transition-metal-catalyzed enantioselective heteroatom-hydrogen bond insertion reactions[J].Accounts of Chemical Research，2012，45（8）：1365-1377.
[30]Liang Y，Zhou H L，Yu Z X.Why is copper（Ⅰ）complex more competent than dirhodium（Ⅱ）complex in catalytic asymmetric O—H insertion reactions？ A computational study of the metal carbenoid O—H insertion into water[J].Journal of the American Chemical Society，2009，131（49）：17783-17785.
[31]Wang B，Qiu D，Zhang Y，et al.Recent advances in C（sp3）—H bond functionalization viametal-carbene insertions[J].Beilstein Journal of Organic Chemistry，2016，12：796-804.
[32]Liao K B，Negretti S，Musaev D G，et al.Site-selective and stereoselective functionalization of unactivated C—H bonds[J].Nature，2016，533（7602）：230-234.
[33]Liao K B，Pickel T C，Boyarskikh V，et al.Site-selective and stereoselective functionalization of non-activated tertiary C—H bonds[J].Nature，2017，551（7682）：609-613.
[34]Liao K B，Yang Y F，Li Y Z，et al.Design of catalysts for site-selective and enantioselective functionalization of non-activated primary C—H bonds[J].Nature Chemistry，2018，10（10）：1048-1055.
[35]Cui Y，Jiao Z D，Gong J X，et al.Development of new stereodiverse diaminocyclitols as inhibitors of influenza virus neuraminidase[J].Organic Letters，2010，12（1）：4-7.
[36]Zhou Q，Li S C，Zhang Y，et al.Rhodium（Ⅱ）-or copper（Ⅰ）-catalyzed formal intramolecular carbene insertion into vinylic C（sp2）—H bonds：Access to substituted 1H-indenes[J].Angewandte Chemie International Edition，2017，56（50）：16013-16017.
[37]Doyle M P，Brandes B D，Kazala A P，et al.Chiral rhodium（Ⅱ）carboxamides.A new class of catalysts for enantioselective cyclopropanation reactions[J].Tetrahedron Letters，1990，31（46）：6613-6616.
[38]Hansen J，Davies H M L.High symmetry dirhodium（Ⅱ）paddlewheel complexes as chiral catalysts[J].Coordination Chemistry Reviews，2008，252（5-7）：545-555.
[39]Huang L Y，Chen Y，Gao G Y，et al.Diastereoselective and enantioselective cyclopropanation of alkenes catalyzed by cobalt porphyrins[J].The Journal of Organic Chemistry，2003，68（21）：8179-8184.
[40]Chen Y，Fields K B，Zhang X P.Bromoporphyrins as versatile synthons for modular construction of chiral porphyrins：Cobalt-catalyzed highly enantioselective and diastereoselective cyclopropanation[J].Journal of the American Chemical Society，2004，126（45）：14718-14719.
[41]Zhang J，Jiang J W，Xu D M，et al.Interception of cobalt-based carbene radicals with α-aminoalkyl radicals：A tandem reaction for the construction of β-ester-γ-amino ketones[J].Angewandte Chemie International Edition，2015，54（4）：1231-1235.
[42]Das B G，Chirila A，Tromp M，et al.CoⅢ-carbene radical approach to substituted 1H-indenes[J].Journal of the American Chemical Society，2016，138（28）：8968-8975.
[43]Roy S，Das S K，Chattopadhyay B.Cobalt（Ⅱ）-based metalloradical activation of 2-（diazomethyl）pyridines for radical transannulation and cyclopropanation[J].Angewandte Chemie International Edition，2018，57（8）：2238-2243.
[44]Zhou L，Shi Y，Xiao Q，et al.CuBr-catalyzed coupling of N-tosylhydrazones and terminal alkynes：Synthesis of benzofurans and indoles[J].Organic Letters，2011，13（5）：968-971.
[45]Paul N D，Mandal S，Otte M，et al.Metalloradical approach to 2H-chromenes[J].Journal of the American Chemical Society，2014，136（3）：1090-1096.
[46]Wang Y，Wen X，Cui X，et al.Enantioselective radical cyclization for construction of 5-membered ring structures by metalloradical C—H alkylation[J].Journal of the American Chemical Society，2018，140（14）：4792-4796.
[47]Benitez D，Shapiro N D，Tkatchouk E，et al.A bonding model for gold（Ⅰ）carbene complexes[J].Nature Chemistry，2009，1（6）：482-486.
[48]Obradors C，Echavarren A M.Gold-catalyzed rearrangements and beyond[J].Accounts of Chemical Research，2014，47（3）：902-912.
[49]Shiroodi R K，Gevorgyan V.Metal-catalyzed double migratory cascade reactions of propargylic esters and phosphates[J].Chemical Society Reviews，2013，42（12）：4991-5001.
[50]Davies P W，Garzón M.Nucleophilic nitrenoids through π-acid catalysis：Providing a common basis for rapid access into diverse nitrogen heterocycles[J].Asian Journal of Organic Chemistry，2015，4（8）：694-708.
[51]Gorin D J，Davis N R，Toste F D.Gold（Ⅰ）-catalyzed intramolecular acetylenic Schmidt reaction[J].Journal of the American Chemical Society，2005，127（32）：11260-11261.
[52]Zhang L M.A non-diazo approach to α-oxo gold carbenes viagold-catalyzed alkyne oxidation[J].Accounts of Chemical Research，2014，47（3）：877-888.
[53]Xia Y，Qiu D，Wang J B.Transition-metal-catalyzed cross-couplings through carbene migratory insertion[J].Chemical Reviews，2017，117（23）：13810-13889.(https://www.daowen.com)
[54]Greenman K L，Carter D S，van Vranken D L.Palladium-catalyzed insertion reactions of trimethylsilyldiazomethane[J].Tetrahedron，2001，57（24）：5219-5225.
[55]Barluenga J，Moriel P，Valdés C，et al.N-tosylhydrazones as reagents for cross-coupling reactions：A route to polysubstituted olefins[J].Angewandte Chemie International Edition，2007，46（29）：5587-5590.
[56]Peng C，Wang Y，Wang J B.Palladium-catalyzed cross-coupling of α-diazocarbonyl compounds with arylboronic acids[J].Journal of the American Chemical Society，2008，130（5）：1566-1567.
[57]Zhou L，Ye F，Ma J C，et al.Palladium-catalyzed oxidative cross-coupling of N-tosylhydrazones or diazoesters with terminal alkynes：A route to conjugated enynes[J].Angewandte Chemie International Edition，2011，50（15）：3510-3514.
[58]Wang P S，Lin H C，Zhou X L，et al.Palladium（Ⅱ）/Lewis acid synergistically catalyzed allylic C—H olefination[J].Organic Letters，2014，16（12）：3332-3335.
[59]Xiao Q，Wang B L，Tian L M，et al.Palladium-catalyzed three-component reaction of allenes，aryl iodides，and diazo compounds：Approach to 1，3-dienes[J].Angewandte Chemie International Edition，2013，52（35）：9305-9308.
[60]Liu Z X，Xia Y，Zhou S Y，et al.Pd-catalyzed cyclization and carbene migratory insertion：New approach to 3-vinylindoles and 3-vinylbenzofurans[J].Organic Letters，2013，15（19）：5032-5035.
[61]Zhou L，Ye F，Zhang Y，et al.Cyclopropylmethyl palladium species from carbene migratory insertion：New routes to 1，3-butadienes[J].Organic Letters，2012，14（3）：922-925.
[62]Zhou L，Ye F，Zhang Y，et al.Pd-catalyzed three-component coupling of N-tosylhydrazone，terminal alkyne，and aryl halide[J].Journal of the American Chemical Society，2010，132（39）：13590-13591.
[63]Xia Y，Hu F D，Liu Z X，et al.Palladium-catalyzed diarylmethyl C（sp3）—C（sp2）bond formation：A new coupling approach toward triarylmethanes[J].Organic Letters，2013，15（7）：1784-1787.
[64]Liu Z X，Tan H C，Fu T R，et al.Pd（0）-catalyzed carbene insertion into Si—Si and Sn—Sn bonds[J].Journal of the American Chemical Society，2015，137（40）：12800-12803.
[65]Xia Y，Qu S L，Xiao Q，et al.Palladium-catalyzed carbene migratory insertion using conjugated ene-yne-ketones as carbene precursors[J].Journal of the American Chemical Society，2013，135（36）：13502-13511.
[66]Xia Y，Xia Y M，Ge R，et al.Oxidative cross-coupling of allenyl ketones and organoboronic acids：Expeditious synthesis of highly substituted furans[J].Angewandte Chemie International Edition，2014，53（15）：3917-3921.
[67]Gao Y P，Wu G J，Zhou Q，et al.Palladium-catalyzed oxygenative cross-coupling of ynamides and benzyl bromides by carbene migratory insertion[J].Angewandte Chemie International Edition，2018，57（10）：2716-2720.
[68]Wang K，Ping Y F，Chang T W，et al.Palladium-catalyzed [3+3]annulation of vinyl chromium（0）carbene complexes through carbene migratory insertion/tsuji-trost reaction[J].Angewandte Chemie International Edition，2017，56（42）：13140-13144.
[69]Suárez A，Fu G C.A straightforward and mild synthesis of functionalized 3-alkynoates[J].Angewandte Chemie International Edition，2004，43（27）：3580-3582.
[70]Xiao Q，Xia Y，Li H，et al.Coupling of N-tosylhydrazones with terminal alkynes catalyzed by copper（Ⅰ）：Synthesis of trisubstituted allenes[J].Angewandte Chemie International Edition，2011，50（5）：1114-1117.
[71]Hossain M L，Ye F，Zhang Y，et al.CuI-catalyzed cross-coupling of N-tosylhydrazones with terminal alkynes：Synthesis of 1，3-disubstituted allenes[J].The Journal of Organic Chemistry，2013，78（3）：1236-1241.
[72]Ye F，Wang C P，Ma X S，et al.Synthesis of terminal allenes through copper-mediated cross-coupling of ethyne with N-tosylhydrazones or α-diazoesters[J].The Journal of Organic Chemistry，2015，80（1）：647-652.
[73]Ye F，Hossain M L，Xu Y，et al.Synthesis of allyl allenes through three-component cross-coupling reaction of N-tosylhydrazones，terminal alkynes，and allyl halides[J].Chemistry — An Asian Journal，2013，8（7）：1404-1407.
[74]Chu W D，Zhang L，Zhang Z K，et al.Enantioselective synthesis of trisubstituted allenes viaCu（Ⅰ）-catalyzed coupling of diazoalkanes with terminal alkynes[J].Journal of the American Chemical Society，2016，138（44）：14558-14561.
[75]Hossain M L，Ye F，Liu Z X，et al.Synthesis of phenanthrenes through copper-catalyzed cross-coupling of N-tosylhydrazones with terminal alkynes[J].The Journal of Organic Chemistry，2014，79（18）：8689-8699.
[76]Ye F，Shi Y，Zhou L，et al.Expeditious synthesis of phenanthrenes viaCuBr2-catalyzed coupling of terminal alkynes and N-tosylhydrazones derived from O-formyl biphenyls[J].Organic Letters，2011，13（19）：5020-5023.
[77]Ye F，Ma X S，Xiao Q，et al.C（sp）—C（sp3）bond formation through Cu-catalyzed cross-coupling of N-tosylhydrazones and trialkylsilylethynes[J].Journal of the American Chemical Society，2012，134（13）：5742-5745.
[78]Zhao X，Wu G J，Zhang Y，et al.Copper-catalyzed direct benzylation or allylation of 1，3-azoles with N-tosylhydrazones[J].Journal of the American Chemical Society，2011，133（10）：3296-3299.
[79]Xu S，Wu G J，Ye F，et al.Copper（Ⅰ）-catalyzed alkylation of polyfluoroarenes through direct C—H bond functionalization[J].Angewandte Chemie International Edition，2015，54（15）：4669-4672.
[80]Zhang Z K，Zhou Q，Ye F，et al.Copper（Ⅰ）-catalyzed three-component coupling of N-tosylhydrazones，alkynes and azides：Synthesis of trisubstituted 1，2，3-triazoles[J].Advanced Synthesis & Catalysis，2015，357（10）：2277-2286.
[81]Tsoi Y T，Zhou Z Y，Yu W Y.Rhodium-catalyzed cross-coupling reaction of arylboronates and diazoesters and tandem alkylation reaction for the synthesis of quaternary α，α-heterodiaryl carboxylic esters[J].Organic Letters，2011，13（19）：5370-5373.
[82]Xia Y，Liu Z，Feng S，et al.Rh（Ⅰ）-catalyzed cross-coupling of α-diazoesters with arylsiloxanes[J].Organic Letters，2015，17（4）：956-959.
[83]Liu Z，Xia Y，Feng S，et al.RhⅠ-catalyzed stille-type coupling of diazoesters with aryl trimethylstannanes[J].Australian Journal of Chemistry，2015，68（9）：1379-1384.
[84]Xia Y，Liu Z X，Liu Z，et al.Formal carbene insertion into C—C bond：Rh（Ⅰ）-catalyzed reaction of benzocyclobutenols with diazoesters[J].Journal of the American Chemical Society，2014，136（8）：3013-3015.
[85]Xia Y，Feng S，Liu Z，et al.Rhodium（Ⅰ）-catalyzed sequential C（sp）—C（sp3）and C（sp3）—C（sp3）bond formation through migratory carbene insertion[J].Angewandte Chemie International Edition，2015，54（27）：7891-7894.
[86]Feng S，Mo F Y，Xia Y，et al.Rhodium（Ⅰ）-catalyzed C—C bond activation of siloxyvinylcyclopropanes with diazoesters[J].Angewandte Chemie International Edition，2016，55（49）：15401-15405.
[87]Chan W W，Lo S F，Zhou Z Y，et al.Rh-catalyzed intermolecular carbenoid functionalization of aromatic C—H bonds by α-diazomalonates[J].Journal of the American Chemical Society，2012，134（33）：13565-13568.
[88]Hu F D，Xia Y，Ye F，et al.Rhodium（Ⅲ）-catalyzed orthoalkenylation of N-phenoxyacetamides with N-tosylhydrazones or diazoesters through C—H activation[J].Angewandte Chemie International Edition，2014，53（5）：1364-1367.
[89]Zhang H，Wang K，Wang B，et al.Rhodium（Ⅲ）-catalyzed transannulation of cyclopropenes with N-phenoxyacetamides through C—H activation[J].Angewandte Chemie International Edition，2014，53（48）：13234-13238.
[90]Yao T，Hirano K，Satoh T，et al.Nickel-and cobalt-catalyzed direct alkylation of azoles with N-tosylhydrazones bearing unactivated alkyl groups[J].Angewandte Chemie International Edition，2012，51（3）：775-779.
[91]Xia Y，Liu Z，Feng S，et al.Ir（Ⅲ）-catalyzed aromatic C—H bond functionalization viametal carbene migratory insertion[J].The Journal of Organic Chemistry，2015，80（1）：223-236.
[92]Zhao D B，Kim J H，Stegemann L，et al.Cobalt（Ⅲ）-catalyzed directed C—H coupling with diazo compounds：Straightforward access towards extended π-systems[J].Angewandte Chemie International Edition，2015，54（15）：4508-4511.
[93]Li Y Y，Qi Z S，Wang H，et al.Ruthenium（Ⅱ）-catalyzed C—H activation of imidamides and divergent couplings with diazo compounds：Substrate-controlled synthesis of indoles and 3H-indoles[J].Angewandte Chemie International Edition，2016，55（39）：11877-11881.
[94]Liu L J，Song Y，Li H.Carbene polymerization：Characterization of poly （carballyloxycarbene）[J].Polymer International，2002，51（10）：1047-1049.
[95]Ihara E，Akazawa M，Itoh T，et al.π-AllylPdCl-based initiating systems for polymerization of alkyl diazoacetates：Initiation and termination mechanism based on analysis of polymer chain end structures[J].Macromolecules，2012，45（17）：6869-6877.
[96]Hetterscheid D G H，Hendriksen C，Dzik W I，et al.Rhodium-mediated stereoselective polymerization of “carbenes”[J].Journal of the American Chemical Society，2006，128（30）：9746-9752.
[97]Chu J H，Xu X H，Kang S M，et al.Fast living polymerization and helix-sense-selective polymerization of diazoacetates using air-stable palladium（Ⅱ）catalysts[J].Journal of the American Chemical Society，2018，140（50）：17773-17781.
[98]Miki K，Washitake Y，Ohe K，et al.Polyaddition and polycondensation reactions of （2-furyl）carbenoid as step-growth polymerization strategies：Synthesis of furylcyclopropane-and furfurylidene-containing polymers[J].Angewandte Chemie International Edition，2004，43（14）：1857-1860.
[99]Nzulu F，Bontemps A，Robert J，et al.Gold-catalyzed polymerization based on carbene polycyclopropanation[J].Macromolecules，2014，47（19）：6652-6656.
[100]Ihara E，Saiki K，Goto Y，et al.Polycondensation of bis （diazocarbonyl）compounds with aromatic diols and cyclic ethers：Synthesis of new type of polyetherketones[J].Macromolecules，2010，43（10）：4589-4598.
[101]Ihara E，Hara Y，Itoh T，et al.Three-component polycondensation of bis （diazoketone）with dicarboxylic acids and cyclic ethers：Synthesis of new types of poly（ester ether ketone）s[J].Macromolecules，2011，44（15）：5955-5960.
[102]Shimomoto H，Mukai H，Bekku H，et al.Ru-catalyzed polycondensation of dialkyl 1，4-phenylenebis （diazoacetate）with dianiline：Synthesis of well-defined aromatic polyamines bearing an alkoxycarbonyl group at the adjacent carbon of each nitrogen in the main chain framework[J].Macromolecules，2017，50（23）：9233-9238.
[103]Zhou Q，Gao Y P，Xiao Y Y，et al.Palladium-catalyzed carbene coupling of N-tosylhydrazones and arylbromides to synthesize cross-conjugated polymers[J].Polymer Chemistry，2019，10（5）：569-573.
[1] ee%，enantiomeric excess percent，对映体过量百分比。
[2] 1atm=101325Pa。
