Abstract
A computational study with the B3LYP functional was carried out to elucidate the mechanisms of AuCl3- and AgOTf-catalyzed cyclization of 1-(indol-2-yl)-3-alkyn-1-ols. The theoretical studies suggested that the two main processes, cycloaddition and hydrogen-transfer, are included in all possible reaction pathways. Calculations revealed that AuCl3 is more effective in catalytic ability than AgOTf to catalyze the cyclization of 1-(indol-2-yl)-3-alkyn-1-ols into carbazole derivatives. More importantly, we found that the ligands of catalysts, Cl− and OTf−, are critical in a stepwise proton-transport process involved in intramolecular nucleophilic addition because they act as a proton shuttle to lower the activation free energy barrier of the rate-determining step. The theoretical discovery of the role of ligands of catalysts in hydrogen shift process suggests that AuCl3- and AgOTf-catalyzed cyclization of 1-(indol-2-yl)-3-alkyn-1-ols can be accelerated when ligands with the property of nucleophile are used. Our theoretical calculations reproduced the experimental results very well. The present study is expected to help understand other transition metal-catalyzed reactions and to give guidance for future design of new catalysts.
Similar content being viewed by others
References
Laronze M, Boisbrun M, Léonce S, Pfeiffer B, Renard P, Lozach O, Meijer L, Lansiaux A, Bailly C, Sapi J (2005) Synthesis and anticancer activity of new pyrrolocarbazoles and pyrrolo-β-carbolines. Bioorg Med Chem 13(6):2263–2283
Howard-Jones AR, Walsh CT (2006) Staurosporine and rebeccamycin aglycones are assembled by the oxidative action of StaP, StaC, and RebC on chromopyrrolic acid. J Am Chem Soc 128(37):12289–12298
Cho SH, Yoon J, Chang S (2011) Intramolecular oxidative C−N bond formation for the synthesis of carbazoles: comparison of reactivity between the copper-catalyzed and metal-free conditions. J Am Chem Soc 133(15):5996–6005
Justin Thomas K, Lin JT, Tao Y-T, Ko C-W (2001) Light-emitting carbazole derivatives: potential electroluminescent materials. J Am Chem Soc 123(38):9404–9411
Huang J, Niu Y, Yang W, Mo Y, Yuan M, Cao Y (2002) Novel electroluminescent polymers derived from carbazole and benzothiadiazole. Macromol 35(16):6080–6082
Sanda F, Nakai T, Kobayashi N, Masuda T (2004) Synthesis of polyacetylenes having pendant carbazole groups and their photo-and electroluminescence properties. Macromol 37(8):2703–2708
Häussler M, Liu J, Zheng R, Lam JWY, Qin A, Tang BZ (2007) Synthesis, thermal stability, and linear and nonlinear optical properties of hyperbranched polyarylenes containing carbazole and/or fluorene moieties. Macromol 40(6):1914–1925
Holmes R, Forrest S, Tung Y-J, Kwong R, Brown J, Garon S, Thompson M (2003) Blue organic electrophosphorescence using exothermic host–guest energy transfer. Appl Phys Lett 82(15):2422–2424
Cai X, Padmaperuma AB, Sapochak LS, Vecchi PA, Burrows PE (2008) Electron and hole transport in a wide bandgap organic phosphine oxide for blue electrophosphorescence. Appl Phys Lett 92:083308
Su S-J, Sasabe H, Takeda T, Kido J (2008) Pyridine-containing bipolar host materials for highly efficient blue phosphorescent OLEDs. Chem Mater 20(5):1691–1693
Chou HH, Cheng CH (2010) A highly efficient universal bipolar host for blue, green, and red phosphorescent OLEDs. Adv Mater 22(22):2468–2471
Marion N, Díez‐González S, de Frémont P, Noble AR, Nolan SP (2006) AuI‐catalyzed tandem [3, 3] rearrangement–intramolecular hydroarylation: mild and efficient formation of substituted indenes. Angew Chem 118(22):3729–3732
Shen HC (2008) Recent advances in syntheses of heterocycles and carbocycles via homogeneous gold catalysis. Part 1: Heteroatom addition and hydroarylation reactions of alkynes, allenes, and alkenes. Tetrahedron 64(18):3885–3903
Pastine SJ, Youn SW, Sames D (2003) PtIV-catalyzed cyclization of arene-alkyne substrates via intramolecular electrophilic hydroarylation. Org Lett 5(7):1055–1058
Nevado C, Echavarren AM (2005) Intramolecular hydroarylation of alkynes catalyzed by platinum or gold: mechanism and endo selectivity. Chem Eur J 11(10):3155–3164
Menon RS, Findlay AD, Bissember AC, Banwell MG (2009) The Au (I)-catalyzed intramolecular hydroarylation of terminal alkynes under mild conditions: application to the synthesis of 2 H-chromenes, coumarins, benzofurans, and dihydroquinolines. J Org Chem 74(22):8901–8903
Schipper DJ, Hutchinson M, Fagnou K (2010) Rhodium (III)-catalyzed intermolecular hydroarylation of alkynes. J Am Chem Soc 132(20):6910–6911
de Mendoza P, Echavarren AM (2013) Intramolecular hydroarylation of alkynes. Modern gold catalyzed synthesis. Wiley-VCH, Weinheim doi:10.1002/9783527646869.ch5
Zhou W, Yang Y, Wang Z, Deng G-J (2014) Rhodium-catalyzed intermolecular hydroarylation of internal alkynes with N-1-phenylbenzotriazoles. Org Biomol Chem 12(2):251–254
Qiu Y, Kong W, Fu C, Ma S (2012) Carbazoles via AuCl3-Catalyzed Cyclization of 1-(Indol-2-yl)-3-alkyn-1-ols. Org Lett 14(24):6198–6201
Hashmi ASK, Yang W, Rominger F (2012) Gold (I)‐catalyzed rearrangement of 3‐silyloxy‐1, 5‐enynes: an efficient synthesis of benzo [b] thiophenes, dibenzothiophenes, dibenzofurans, and indole derivatives. Chem Eur J 18(21):6576–6580
Hashmi ASK, Blanco MC, Fischer D, Bats JW (2006) Gold catalysis: evidence for the In‐situ reduction of gold (III) during the cyclization of allenyl carbinols. Eur J Org Chem 2006(6):1387–1389
Kong W, Fu C, Ma S (2012) Efficient synthesis of carbazoles via PtCl2-catalyzed RT cyclization of 1-(indol-2-yl)-2, 3-allenols: scope and mechanism. Org Biomol Chem 10(10):2164–2173
Hashmi ASK, Yang W, Rominger F (2011) Gold (I)‐catalyzed formation of benzo [b] furans from 3‐Silyloxy‐1, 5‐enynes. Angew Chem Int Ed 50(25):5762–5765
Xia Y, Dudnik AS, Gevorgyan V, Li Y (2008) Mechanistic insights into the gold-catalyzed cycloisomerization of bromoallenyl ketones: ligand-controlled regioselectivity. J Am Chem Soc 130(22):6940–6941
Zuccaccia D, Belpassi L, Tarantelli F, Macchioni A (2009) Ion pairing in cationic olefin − gold (I) complexes. J Am Chem Soc 131(9):3170–3171
Brouwer C, He C (2006) Efficient gold‐catalyzed hydroamination of 1, 3‐dienes. Angew Chem 118(11):1776–1779
Hamilton GL, Kang EJ, Mba M, Toste FD (2007) A powerful chiral counterion strategy for asymmetric transition metal catalysis. Science 317(5837):496–499
Döpp R, Lothschütz C, Wurm T, Pernpointner M, Keller S, Rominger F, Hashmi ASK (2011) Gold catalysis: hydrolysis of di (alkoxy) carbenium ion intermediates as a sensor for the electronic properties of gold (I) complexes. Organomet 30(21):5894–5903
Kong W, Fu C, Ma S (2009) An efficient synthesis of carbazoles from PtCl2-catalyzed cyclization of 1-(indol-2-yl)-2, 3-allenols. Chem Commun 30:4572–4574
Alcaide B, Almendros P, Alonso JM, Fernández I (2012) Palladium-catalyzed carbocyclization–cross-coupling reactions of two different allenic moieties: synthesis of 3-(buta-1, 3-dienyl) carbazoles and mechanistic insights. Chem Commun 48(52):6604–6606
Yao T, Zhang X, Larock RC (2004) AuCl3-catalyzed synthesis of highly substituted furans from 2-(1-alkynyl)-2-alken-1-ones. J Am Chem Soc 126(36):11164–11165
Zhang J, Shen W, Li L, Li M (2009) Gold (I)-catalyzed cycloaddition of 1-(1-alkynyl) cyclopropyl ketones with nucleophiles to yield substituted furans: a DFT study. Organomet 28(11):3129–3139
Hashmi ASK (2010) Homogeneous gold catalysis beyond assumptions and proposals—characterized intermediates. Angew Chem Int Ed 49(31):5232–5241
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery JJA, Vreven T, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski J, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson BG, Chen W, Wong MW, Gonzalez C, Pople JA (2009) GAUSSIAN 09, revision C01. Gaussian Inc, Wallingford
Becke AD (1993) Density‐functional thermochemistry. III. The role of exact exchange. J Chem Phys 98:5648
Lee C, Yang W, Parr RG (1988) Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B 37(2):785
Krishnan R, Binkley JS, Seeger R, Pople JA (1980) Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions. J Chem Phys 72:650
Hay PJ, Wadt WR (1985) Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals. J Chem Phys 82:299
Wu Y-D, Yu Z-X (2001) A theoretical study on the mechanism and diastereoselectivity of the Kulinkovich hydroxycyclopropanation reaction. J Am Chem Soc 123(24):5777–5786
Yu Z-X, Wender PA, Houk K (2004) On the mechanism of [Rh (CO) 2Cl] 2-catalyzed intermolecular (5+ 2) reactions between vinylcyclopropanes and alkynes. J Am Chem Soc 126(30):9154–9155
Gonzalez C, Schlegel HB (1989) An improved algorithm for reaction path following. J Chem Phys 90:2154
Gonzalez C, Schlegel HB (1990) Reaction path following in mass-weighted internal coordinates. J Phys Chem 94(14):5523–5527
Barone V, Cossi M, Tomasi J (1998) Geometry optimization of molecular structures in solution by the polarizable continuum model. J Comput Chem 19(4):404–417
Takano Y, Houk K (2005) Benchmarking the conductor-like polarizable continuum model (CPCM) for aqueous solvation free energies of neutral and ionic organic molecules. J Chem Theor Comput 1(1):70–77
Wiberg KB (1968) Application of the pople-santry-segal CNDO method to the cyclopropylcarbinyl and cyclobutyl cation and to bicyclobutane. Tetrahedron 24(3):1083–1096
Reed AE, Curtiss LA, Weinhold F (1988) Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint. Chem Rev 88(6):899–926
Bader RF (1990) Atoms in molecules. Wiley Online Library
Biegler-König F, Schönbohm J, Derdau R, Bayles D, Bader R (2002) AIM2000, version 2.0. McMaster University
Biegler Konig F, Schonbohm J, Bayles D (2001) Software news and updates AIM2000. J Comput Chem 22:545–559
Liu Y, Zhang D, Bi S, Liu C (2013) Theoretical investigation on Pt (ii)-and Au (i)-mediated cycloisomerizations of propargylic 3-indoleacetate:[3+ 2]-versus [2+ 2]-cycloaddition products. Org Biomol Chem 11(2):336–343
Shaler TA, Borchardt D, Morton TH (1999) Competing 1, 3-and 1, 2-hydrogen shifts in gaseous fluoropropyl cations. J Am Chem Soc 121(34):7907–7913
Vrček IV, Vrček V, Siehl H-U (2002) Quantum chemical study of degenerate hydride shifts in acyclic tertiary carbocations. J Phys Chem A 106(8):1604–1611
Kraka E, Cremer D (2002) Mechanism and dynamics of organic reactions: 1, 2‐H shift in methylchlorocarbene. J Phys Org Chem 15(8):431–447
Nishizawa M, Yadav A, Iwamoto Y, Imagawa H (2004) Experimental and theoretical approaches into the C-and D-ring problems of sterol biosynthesis. Hydride shift versus C–C bond migration due to cation conformational changes controlled by the counteranion. Tetrahedron 60(41):9223–9234
Hayase S, Hrovat DA, Borden WT (2004) A B3LYP study of the effects of phenyl substituents on 1, 5-hydrogen shifts in 3-(Z)-1, 3-pentadiene provides evidence against a chameleonic transition structure. J Am Chem Soc 126(32):10028–10034
Hess BA, Baldwin JE (2002) [1, 5] Sigmatropic hydrogen shifts in cyclic 1, 3-dienes. J Org Chem 67(17):6025–6033
Lemière G, Gandon V, Agenet N, Goddard JP, de Kozak A, Aubert C, Fensterbank L, Malacria M (2006) Gold (I)‐and gold (III)‐catalyzed cycloisomerization of allenynes: a remarkable halide effect. Angew Chem 118(45):7758–7761
Vrček V, Vinkovič Vrček I, Siehl H-U (2006) Quantum chemical study of solvent and substituent effects on the 1, 5-hydride shift in 2, 6-dimethyl-2-heptyl cations. J Phys Chem A 110(5):1868–1874
Hashmi ASK, Braun I, Rudolph M, Rominger F (2012) The role of gold acetylides as a selectivity trigger and the importance of gem-diaurated species in the gold-catalyzed hydroarylating-aromatization of arene-diynes. Organomet 31(2):644–661
Hashmi ASK, Wieteck M, Braun I, Noesel P, Jongbloed L, Rudolph M, Rominger F (2012) Gold‐catalyzed synthesis of dibenzopentalenes–evidence for gold vinylidenes. Adv Synth Catal 354(4):555–562
Hashmi ASK, Braun I, Nösel P, Schädlich J, Wieteck M, Rudolph M, Rominger F (2012) Simple gold‐catalyzed synthesis of benzofulvenes—gem‐diaurated species as “instant dual‐activation” precatalysts. Angew Chem Int Ed 51(18):4456–4460
Hashmi ASK, Wieteck M, Braun I, Rudolph M, Rominger F (2012) Gold vinylidene complexes: intermolecular C (sp3)-H insertions and cyclopropanations pathways. Angew Chem Int Ed 51(42):10633–10637
Hansmann MM, Rudolph M, Rominger F, Hashmi ASK (2013) Mechanistic switch in dual gold catalysis of diynes: C (sp3)–H activation through bifurcation—vinylidene versus carbene pathways. Angew Chem Int Ed 52(9):2593–2598
Norberg D, Larsson P-E, Salhi-Benachenhou N (2008) Rearrangement and hydrogen scrambling pathways of the toluene radical cation: a computational study. J Phys Chem A 112(20):4694–4702
Benfatti F, Bottoni A, Cardillo G, Fabbroni S, Gentilucci L, Stenta M, Tolomelli A (2008) The cycloaddition reaction between α‐bromo vinylketenes and imines: a combined experimental and theoretical study. Adv Synth Catal 350(4‐15):2261–2273
Krauter CM, Hashmi ASK, Pernpointner M (2010) A new insight into gold (I)‐catalyzed hydration of alkynes: proton transfer. ChemCatChem 2(10):1226–1230
Bucher J, Wurm T, Nalivela KS, Rudolph M, Rominger F, Hashmi ASK (2014) Cyclization of gold acetylides: synthesis of vinyl sulfonates via gold vinylidene complexes. Angew Chem Int Ed doi:10.1002/anie.201310280
Acknowledgments
We acknowledge generous financial support from “the Fundamental Research Funds for the Central Universities (grant no. XDJK2013A008) “.
Supporting information
Structural parameters optimized by B97D functional, intrinsic reaction coordinate of all the intermediates and transition states, and so on.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
ESM 1
(DOC 2.28 mb)
Rights and permissions
About this article
Cite this article
Shao, J., He, R., Shen, W. et al. Mechanism of AuCl3-catalyzed cyclization of 1-(Indol-2-yl)-3-alkyn-1-ols: a DFT study. J Mol Model 20, 2239 (2014). https://doi.org/10.1007/s00894-014-2239-z
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s00894-014-2239-z