Cross-benzoin and Stetter-type reactions mediated by KOtBu-DMF via an electron-transfer process

Pier Giovannini

Cross-benzoin and Stetter-type reactions mediated by KOtBu-DMF via an electron-transfer process

Organic & Biomolecular Chemistry, 2016

The KOtBu-DMF system promotes benzoin- and Stetter-like reactions of alpha-diketone donors through a double electron-transfer-based mechanism....Read more

S1 Electronic Supporting Information Cross-Benzoin and Stetter-Type Reactions Mediated by KOtBu-DMF via Electron-Transfer process Daniele Ragno, a Anna Zaghi, a Graziano Di Carmine, a Pier Paolo Giovannini, a Olga Bortolini, a Marco Fogagnolo, a Alessandra Molinari, a Alessandro Venturini,* b and Alessandro Massi* a a Dipartimento di Scienze Chimiche e Farmaceutiche, Università di Ferrara, Via Fossato di Mortara 17, I-44121 Ferrara (Italy) b ISOF-CNR, Area della Ricerca di Bologna, Via P. Gobetti 101, I-40129 Bologna (Italy) alessandro.massi@unife.it; alessandro.venturini@isof.cnr.it Table of Contents MS experiments (Figures S1-S2) S2 EPR experiments (Figures S3-S5) S3 Computational methods, Cartesian coordinates and energies in Hartree for species calculated S5 NMR spectra of new compounds S16 References S22 Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is © The Royal Society of Chemistry 2016

S2 Mass spectrometric experiments The mass spectrometric investigations were carried out on a LCQ Duo (ThermoQuest, San Jose, CA, USA), equipped with an electrospray ionization source operating in negative-ion mode. Instrumental parameters: capillary voltage -10 V, spray voltage 4.50 kV, capillary temperature of 150 °C, mass scan range from m/z 50 to 1200; N 2 was used as sheath gas. The samples were injected into the spectrometer by a syringe pump at a constant flow rate of 8 µL/min using the appropriate eluting solvent. Figure S1. Full scan spectrum of the benzoin-like reaction of 1a (0.5 M), 2a (0.5 M) in DMF with KOtBu (0.125 M) showing the presence of anion E (m/z 90) and isobaric species I-III(E) (m/z 300). Figure S2. MS/MS mass spectrum of the deuterated adduct III(E)-d obtained from DMF-d 7 solutions of 1a (0.5 M), 2a (0.5 M) and KOtBu (0.125 M).

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is © The Royal Society of Chemistry 2016 Electronic Supporting Information Cross-Benzoin and Stetter-Type Reactions Mediated by KOtBu-DMF via Electron-Transfer process Daniele Ragno,a Anna Zaghi,a Graziano Di Carmine,a Pier Paolo Giovannini,a Olga Bortolini,a Marco Fogagnolo,a Alessandra Molinari,a Alessandro Venturini,*b and Alessandro Massi*a a Dipartimento di Scienze Chimiche e Farmaceutiche, Università di Ferrara, Via Fossato di Mortara 17, I-44121 Ferrara (Italy) b ISOF-CNR, Area della Ricerca di Bologna, Via P. Gobetti 101, I-40129 Bologna (Italy) alessandro.massi@unife.it; alessandro.venturini@isof.cnr.it Table of Contents MS experiments (Figures S1-S2) S2 EPR experiments (Figures S3-S5) S3 Computational methods, Cartesian coordinates and energies in Hartree for species calculated S5 NMR spectra of new compounds S16 References S22 S1 Mass spectrometric experiments The mass spectrometric investigations were carried out on a LCQ Duo (ThermoQuest, San Jose, CA, USA), equipped with an electrospray ionization source operating in negative-ion mode. Instrumental parameters: capillary voltage -10 V, spray voltage 4.50 kV, capillary temperature of 150 °C, mass scan range from m/z 50 to 1200; N2 was used as sheath gas. The samples were injected into the spectrometer by a syringe pump at a constant flow rate of 8 µL/min using the appropriate eluting solvent. Figure S1. Full scan spectrum of the benzoin-like reaction of 1a (0.5 M), 2a (0.5 M) in DMF with KOtBu (0.125 M) showing the presence of anion E (m/z 90) and isobaric species I-III(E) (m/z 300). Figure S2. MS/MS mass spectrum of the deuterated adduct III(E)-d obtained from DMF-d7 solutions of 1a (0.5 M), 2a (0.5 M) and KOtBu (0.125 M). S2 EPR experiments EPR investigation was carried out with a Bruker ER200 MRD spectrometer calibrated with α,α’diphenylpicrylhydrazyl (dpph, resonance at 3457.41 G, g = 2.0023) and equipped with a TE201 resonator (microwave frequency of 9.4 GHz). A flat quartz cell was used for all the experiments. Samples were DMF solutions containing KOtBu (0.125 M) to which benzyl 1a (0.5 M) and aldehyde 2a (0.5 M) were added stepwise and when necessary. In the case of EPR spin trapping experiments, DMF solutions contain from the beginning a-phenyl-N-tert-butyl nitrone (PBN, 0.5 M) as radical trap. When requested benzyl 1a (0.5 M) and aldehyde 2a (0.5 M) were progressively added. Figure S3. Fixed-field EPR signal intensity of a radical species (g= 2.0017) in time obtained by the addition of aldehyde 2a (0.5 M) to a DMF solution of KOtBu (0.125 M) and of benzil 1a (0.5 M). Figure S4. Fixed-field EPR signal intensity of the paramagnetic adduct [PBN-benzyl anion radical V]• in time. (●) DMF solution containing KOtBu (0.125 M), benzil 1a (0.5 M) and PBN (0.5 M). (▲) the same as before with the addition of aldehyde 2a (0.5 M). S3 Figure S5. Anaerobic EPR spectrum of a DMF solution containing KOtBu (0.125 M) and PBN (0.5 M). S4 Computational methods, Cartesian coordinates and energies in Hartree for species calculated DFT calculations were carried out with the Truhlar M06 hybrid functional,1 together with the 6-31+ G(d,p) basis set within the framework of the Gaussian 09 suite of programs.2 All the molecular structures were fully optimized by using the PCM continuum model (N,N-dimethylformamide and dimethylsulfoxide)3 and the Berny analytical gradient optimization method, whereby the stationary points were characterized by frequency calculation. Thermochemical analysis (free energies DDG) was performed at 298.15 K, starting from the frequency calculations. Electronic energies (E, u.a.), Gibbs free energies (DG, u.a.), and fully optimized structures [M06//631+G(d,p) level using PCM continuum model (N,N-dimethylformamide and dimethylsulfoxide)] are reported in the next pages (pp. S5-S14). S5 Structures of Figure 3 TS reactants- I(E) 1a E = -1013.80292 DG = -1013.53566 E = -689.51998 DG = -689.36149 C O C C C C C C H H H H H C O C C C C C C H H H H H -0.868844 -0.179584 -1.618674 -1.501990 -2.225261 -3.074060 -3.199710 -2.471765 -0.839556 -2.133648 -3.641473 -3.862277 -2.570196 -0.862894 -0.162156 -1.616089 -1.489398 -2.215464 -3.077001 -3.212607 -2.481938 -0.817082 -2.116133 -3.646586 -3.885062 -2.588200 -0.494326 -1.497915 -0.140331 -0.953407 -0.652366 0.456605 1.265450 0.970338 -1.814750 -1.278930 0.690780 2.126359 1.607084 0.480119 1.475682 0.134804 0.946476 0.653801 -0.445295 -1.252632 -0.965940 1.800112 1.279264 -0.672904 -2.105831 -1.601503 C C C C C C C O C O C C C C C C O C N C O C H H H H H H H H H H H H H H H H H H 0.135532 0.254542 -1.078274 -2.213509 -3.357817 -3.372863 -2.245241 -1.098263 -2.178466 -4.240897 -4.270210 -2.260793 -0.221126 1.314478 1.195081 2.528701 3.663867 4.808577 4.824097 3.696547 2.549165 3.628456 5.691604 5.721758 3.712468 1.672084 E E = -324.27277 DG = -324.18874 C -1.605229 -0.848889 -0.290468 N -0.643114 0.221028 -0.429466 C -0.909573 1.279770 0.519908 C 0.764065 -0.252725 -0.407283 O 1.656935 0.680661 -0.576519 H 0.766997 -1.090730 -1.154536 H -2.611920 -0.490390 -0.545750 H -1.354575 -1.670419 -0.974704 H -1.643083 -1.263229 0.736222 H -1.885681 1.736745 0.308411 H -0.930214 0.920469 1.568603 H -0.136215 2.049365 0.433906 O 0.993418 -0.983299 0.872501 H 1.598088 -0.386835 1.333316 1.821514 1.327215 2.170695 3.483801 3.968057 3.132054 -0.051995 -0.358819 -1.182273 -1.020620 -2.515299 -2.710691 -3.992303 -5.090196 -4.904355 -3.623789 0.151896 1.058643 1.444336 2.457524 0.604906 1.954380 2.015011 2.753542 2.071395 3.369520 2.212785 2.869659 1.200565 0.253711 1.784063 4.127214 4.993751 3.508801 1.187340 -3.465813 -5.757355 -6.090269 -4.135237 -1.845847 -1.520647 -1.407429 -1.714647 -2.125374 -2.230668 -1.926074 -0.927358 -0.642629 -1.244954 -2.119887 -0.605025 0.629231 1.157895 0.460918 -0.768748 -1.293616 0.928596 1.652757 2.874280 3.626272 2.110695 2.516949 1.078929 4.500779 3.971580 3.020593 3.426215 1.889024 1.959773 1.309557 -1.619122 -2.359783 -2.545934 -1.999018 -1.255149 -2.252011 -1.316924 0.877613 2.123134 1.179695 -0.987837 0.317222 1.387362 1.167460 -0.133088 -1.209051 0.641901 1.808998 -0.340956 -1.181821 -0.162852 0.469286 0.583810 0.081272 -0.548783 -0.673561 -0.468122 0.168104 -0.561333 0.159978 1.467798 -1.873276 0.368821 -0.431442 1.121878 0.349471 -2.428601 -1.807800 -2.434533 1.886904 2.399392 2.012477 -0.311507 -2.226956 -1.827329 -1.162654 -0.941571 0.178585 1.064181 0.823241 IE E = -1013.81590 DG = -1013.54477 C N C S6 1.521792 0.861926 1.557555 4.081183 -0.044428 2.911482 -0.607532 2.490697 -1.815103 C O O H H H H H H H H C C O C C C C C C H H H H H O C C C C C C H H H H H 0.813878 0.198357 0.105153 1.853188 1.545783 0.979831 2.566770 1.563228 2.610490 1.052532 0.034323 0.223777 -0.930071 0.020773 1.581844 2.472381 3.718583 4.080389 3.188063 1.950021 2.173738 4.407613 5.050739 3.461530 1.257402 -0.731465 -2.324669 -3.283400 -4.601703 -4.985720 -4.042862 -2.720524 -2.974857 -5.329757 -6.016537 -4.338419 -1.989629 1.836714 2.298183 0.774397 1.497104 4.874593 4.446128 3.862886 3.318670 2.208380 1.636103 1.448370 -0.471875 -1.379529 -0.295191 -1.078932 -1.474566 -2.009844 -2.161214 -1.775164 -1.239467 -1.348597 -2.308844 -2.577546 -1.892060 -0.932081 -2.583749 -0.847860 -1.715683 -1.309586 -0.024070 0.846865 0.444272 -2.717913 -1.995612 0.298381 1.850058 1.130846 C C C C O C O N C C H H H H H H H H H H H H H H H H H H 0.356630 1.525667 -0.198065 0.603253 -0.798609 0.830035 0.256011 -2.531682 -1.610492 -2.271166 2.006319 0.599629 0.118707 1.900553 0.225808 1.219015 0.886941 -0.448802 -1.451677 -1.113059 2.257634 1.674651 -0.711069 -2.498561 -1.896349 -0.011788 -0.020478 -0.560633 -0.731525 -0.353633 0.189422 0.351211 -0.847709 -1.158355 -0.482576 0.488210 0.764077 2.784107 3.760914 3.524260 2.311012 0.190718 -0.735624 -1.796247 -0.016046 -0.914965 1.054338 -0.035339 -0.138797 -1.478425 -2.736694 -2.647327 2.107181 4.284581 4.704671 2.964053 0.803370 -1.099946 -2.210259 -1.409988 -1.687546 -0.338929 1.756291 0.663935 1.594855 1.603252 0.608924 -0.622236 -0.859621 0.435418 0.119080 1.004547 0.203330 -0.011938 -0.784573 -1.943897 -1.941584 -0.218860 1.480741 1.443670 -1.824483 -1.399728 0.792599 2.564669 2.134360 -0.915440 0.829044 -1.003033 0.758561 0.032794 -0.617122 -1.819522 -0.699821 II(E) E = -1013.79632 DG = -1013.52900 C C C C C C C O C O C C C C C C O C O N C TS1(E) E = -1013.79682 DG = -1013.52580 C C C C C C C O C O C C -1.554311 -1.595546 -0.984726 -0.342658 1.696794 2.716179 2.721171 3.967036 5.092633 3.999773 -1.991884 -4.469472 -5.661382 -4.350190 -1.866785 0.120233 -1.014972 -2.104190 -2.030431 -0.875252 2.538372 1.825228 5.043639 5.121807 6.022847 3.178718 3.918362 4.948173 -2.512833 -0.622258 -1.191652 -1.766997 -1.323425 -0.239840 -2.447412 -2.088893 0.712734 -3.838978 -2.141330 0.726978 -4.574484 -1.436783 -0.224300 -3.904901 -0.682770 -1.186912 -0.263445 -1.291252 -0.157727 0.326551 -2.385228 0.188497 0.408142 0.035589 -0.125963 0.323981 -0.486361 -1.408817 -0.303509 1.331171 0.130197 -0.905270 1.574837 1.364692 S7 -2.493403 -1.691433 -2.304633 -3.689664 -4.484325 -3.880583 -0.186921 0.437376 0.431595 0.301581 -0.362665 -0.562604 -1.311599 -1.861896 -1.661346 -0.918397 1.731634 2.753974 2.705468 4.006614 5.131728 -1.064633 -1.348821 -1.753215 -1.856899 -1.575847 -1.185298 -1.273851 -2.356857 0.086699 -0.517722 1.336062 1.800423 2.950341 3.652665 3.194977 2.037731 0.343102 -0.621760 -1.596854 0.094124 -0.828938 -1.273116 -0.167604 1.023032 1.112073 0.000313 -1.192722 -0.191336 0.161233 -0.198520 -1.449794 0.034099 1.336891 1.567512 0.494721 -0.805691 -1.033523 0.274553 0.095805 1.068138 0.179110 0.115612 C H H H H H H H H H H H H H H H H H H 4.116249 -1.680571 -4.150746 -5.566756 -4.491932 -2.022597 -0.774782 -2.090565 -2.448546 -1.468480 -0.132407 1.839647 2.619592 5.138050 5.105043 6.063937 5.073744 3.310548 4.077585 1.072443 -1.986911 -2.162030 -1.661436 -0.967666 -0.742364 1.658309 3.736816 4.550840 3.300141 1.247743 -2.066299 -1.073927 -1.413087 -1.527043 -0.256508 1.596172 1.806896 0.595656 H H H H H H H H H H -0.894321 1.884453 2.049272 0.065046 -2.066290 -2.199047 -2.043253 -1.645886 0.674074 2.585555 2.171341 0.850333 -0.911737 -0.826946 0.953879 0.164336 -0.806125 -0.830505 -1.894657 0.812847 1.166258 2.348696 3.126304 2.772728 1.598992 0.405454 -0.953527 -1.763618 -2.070137 0.579215 1.324124 0.769626 -0.609836 -1.086417 -0.198538 1.174525 1.654490 2.366850 -2.961752 -3.776634 -3.744327 -1.305774 -2.158955 -0.575878 1.872424 2.723214 2.651797 4.026052 3.386060 -2.292553 -1.825965 0.661425 -0.263345 0.639910 1.335871 -1.354626 0.242869 -1.091618 1.989493 E = -1013.76818 DG = -1013.50027 C O C C C C C C H H H H H O C O C C C C C C H H H H H C N H O C C H H H H H H H E = -1013.76244 DG = -1013.49344 2.494728 1.552964 1.834329 2.951036 3.854044 3.606542 0.352035 0.399008 1.202527 0.523816 -0.232054 -1.358340 -2.441624 -2.625320 -3.723334 -4.644154 -4.471098 -3.386207 -1.487703 1.528283 0.373971 2.546896 -1.900890 -3.860854 -5.497197 -5.187470 -3.250514 1.154024 3.126235 4.726910 1.287659 -0.094521 -1.228508 -4.548073 -3.112910 -4.203954 -4.537581 -4.290837 -3.153213 -1.231980 III(E) TS2(E) C C C C C C C O C O O C C C C C C C O N C C H H H H H H H H 4.299385 2.324371 2.140252 2.886169 3.410172 2.181183 0.685192 -0.064246 -0.396950 0.187743 -1.247983 -0.240580 0.496338 0.217332 -0.789641 -1.510948 -0.062635 -0.397867 0.425341 1.633960 1.261618 1.107188 0.253507 0.088573 -0.618843 -1.175647 -1.005058 -0.280178 1.724268 -0.277393 -0.629912 0.400162 0.502669 -0.737391 -1.734709 -1.432276 -0.131138 1.289188 0.807081 -1.001071 S8 -1.649869 -1.622223 -2.916362 -2.995764 -4.207610 -5.349904 -5.278578 -4.069499 -2.111712 -4.261500 -6.295078 -6.167398 -4.000994 -0.577393 0.737372 1.382020 1.462018 0.841575 1.577406 2.960990 3.596617 2.876837 -0.234229 1.055991 3.529428 4.677587 3.396882 1.784296 2.823177 2.180162 0.685175 3.470815 2.423799 4.370587 3.775878 2.820675 3.320584 1.753065 1.917273 -0.014915 0.768152 1.773224 0.187135 -1.118425 -1.620029 -0.820838 0.479086 0.977803 -1.750345 -2.638510 -1.212387 1.105032 1.988505 0.086634 0.351785 -0.895626 1.400793 2.442205 3.500364 3.578877 2.548960 1.490602 2.420339 4.277791 4.410243 2.572954 0.703547 -1.495049 -2.435653 -0.720452 -2.137737 -2.904318 -3.543463 -3.470823 -2.051155 -3.559104 -4.088145 -4.254480 -3.163855 -1.473385 -0.746817 -1.440990 -0.221758 0.274829 0.737293 0.715945 0.217675 -0.254268 0.279411 1.113964 1.084604 0.197779 -0.648949 -0.360978 -0.946632 -1.042165 -0.289111 0.450873 0.973538 0.805396 0.099212 -0.430032 0.605626 1.531822 1.215835 -0.036788 -0.974946 0.166883 -0.099932 0.845484 0.795617 1.112333 -0.955338 0.846041 1.729210 1.720040 -1.271952 -0.442489 -1.846417 0.879251 Structures of Figure 6 H IX TS IX-2g E = -689.720593 DG = -689.56415 E = -1035.07880 DG = -1034.81931 C O C C C C C C H H H H H C O C C C C C C H H H H H -0.868841 -0.179583 -1.618643 -1.501947 -2.225244 -3.074088 -3.199733 -2.471737 -0.839493 -2.133620 -3.641544 -3.862281 -2.570125 -0.862945 -0.162210 -1.616113 -1.489387 -2.215432 -3.076995 -3.212637 -2.481980 -0.817034 -2.116058 -3.646588 -3.885111 -2.588277 -0.494330 -1.497910 -0.140329 -0.953410 -0.652381 0.456562 1.265415 0.970330 -1.814736 -1.278935 0.690707 2.126336 1.607110 0.480164 1.475727 0.134843 0.946471 0.653764 -0.445312 -1.252605 -0.965885 1.800079 1.279176 -0.672923 -2.105789 -1.601397 0.135534 0.254564 -1.078296 -2.213531 -3.357827 -3.372850 -2.245239 -1.098275 -2.178485 -4.240912 -4.270178 -2.260787 -0.221157 1.314466 1.195047 2.528703 3.663900 4.808613 4.824109 3.696535 2.549149 3.628517 5.691670 5.721765 3.712428 1.672031 C 0.268305 2.014169 O 1.378007 2.519124 H -0.641292 2.654029 C 0.000000 0.571178 C -1.326963 0.130471 C -1.608624 -1.231679 C -0.561444 -2.151406 C 0.766275 -1.715410 C 1.048926 -0.357074 H -2.133888 0.862274 H -2.639057 -1.576747 H -0.779298 -3.216686 H 1.575657 -2.440839 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 C C C C C C C O C C C C C C C O H H H H H H H H H H C O H C C C C C C H H H H H 2g E = -345.35472 DG = -345.27556 2.074963 -1.373562 -1.014153 -1.943186 -3.165804 -3.501224 -2.593667 0.245319 0.379115 1.481740 2.807352 3.813425 5.066002 5.347227 4.360607 3.099384 1.484507 3.587308 5.825139 6.329035 4.572608 2.305944 -1.673244 -3.860936 -4.451869 -2.842773 -0.694223 0.109835 0.295814 0.918227 -1.212235 -1.373634 -2.618587 -3.733883 -3.582498 -2.337033 -0.503204 -2.718885 -4.705656 -4.442549 -2.208961 0.003485 2.016923 1.217668 1.118646 1.787335 2.583029 2.687096 0.390473 -0.315110 1.090511 0.371231 0.837095 0.235878 -0.845460 -1.318985 -0.723309 2.224217 1.682046 0.608909 -1.314464 -2.161861 -1.070532 0.482385 1.687498 3.112903 3.295834 2.080175 -0.774120 -0.244398 -1.438780 -1.439388 -2.402177 -2.972278 -2.605286 -1.667721 -1.099643 -2.688597 -3.716660 -3.054627 -1.382529 -0.364473 X E = -1035.08485 DG = -1013.82566 S9 0.000000 -0.599740 0.500727 1.547395 1.512587 0.417755 -0.639082 0.587909 1.710711 0.109751 0.159028 -0.702062 -0.742134 0.094111 0.955387 0.986148 -0.392723 -1.348588 -1.427035 0.071713 1.610953 1.642571 2.387773 2.346098 0.386152 -1.508230 -1.442633 -0.896751 -2.083370 -0.502663 -0.648387 0.357357 0.619015 -0.135171 -1.159678 -1.413413 0.943411 1.408222 0.062048 -1.765076 -2.206179 C C C C C C C O C C O C C C C C C O C C C C C C H H H H H H H H H H H H H H H H 2.303724 1.253334 1.488734 2.736318 3.779989 3.553127 -0.089732 -0.368410 -0.193268 -1.502770 -1.590331 1.011402 1.244327 2.404553 3.365182 3.140868 1.973112 -0.370963 -2.786662 -3.765680 -4.983216 -5.250771 -4.290423 -3.065211 -3.554403 -5.724815 -6.204899 -4.498866 -2.304738 1.781582 3.876125 4.271021 2.562926 0.513855 -0.834119 0.674257 2.893032 4.754140 4.355820 2.115087 1.216051 1.507293 2.455525 3.061354 2.740829 1.817443 0.800764 0.334459 -0.346871 -1.102323 -2.332624 -1.271120 -2.008969 -2.763948 -2.804735 -2.086556 -1.336775 0.090793 -0.330520 -0.868392 -0.221348 0.970036 1.504858 0.864798 -1.800594 -0.647084 1.474681 2.426417 1.249474 -0.772132 -2.112912 -3.396166 -3.326216 -1.949773 1.548306 2.711567 3.793742 3.214095 1.568639 0.492564 C -0.225832 -0.472496 0.710539 O -0.526953 -0.400232 2.015942 C -0.118892 0.880865 -0.125837 O -0.693851 0.386892 -1.295902 C 1.212987 1.540590 -0.261260 C 2.033145 1.362836 -1.380942 C 3.302235 1.935710 -1.440047 C 3.782563 2.700399 -0.376401 C 2.969739 2.898544 0.740424 C 1.697820 2.333442 0.789162 C 1.055785 -1.288729 0.442623 C 1.467705 -1.751924 -0.816537 C 2.682696 -2.413317 -0.985125 C 3.532838 -2.627935 0.100464 C 3.139757 -2.178138 1.359126 C 1.915279 -1.527635 1.519379 H -3.446354 -1.139331 -1.917070 H -5.729555 -0.175608 -1.766361 H -6.363892 1.213731 0.203610 H -4.687470 1.627856 1.992406 H -2.385292 0.652298 1.803354 H 1.588470 -1.181373 2.498356 H 3.785806 -2.337641 2.221928 H 4.483652 -3.141174 -0.033743 H 2.971440 -2.761942 -1.976505 H 0.823470 -1.577570 -1.671684 H -0.782334 1.594960 0.412731 H 1.060062 2.506508 1.657068 H 3.324901 3.504812 1.572119 H 4.773821 3.146777 -0.422491 H 3.921945 1.784841 -2.322723 H 1.658421 0.758532 -2.204041 -1.318569 -0.441406 0.562075 0.711110 -0.157186 -1.179561 -0.570382 -1.811115 0.546451 0.307175 0.365297 0.374325 -0.794972 -0.951032 0.061638 1.234885 1.384916 1.828838 0.160847 -0.683755 -0.873384 -0.199545 0.657532 0.834013 -1.204417 -1.546317 -0.337654 1.198168 1.508566 2.296019 2.038473 -0.060481 -1.870882 -1.597171 -0.190406 1.239092 1.502131 -0.047235 -1.873125 -2.109964 XI E = -1035.07839 DG = -1034.81772 C C C C C C C O O C C C C C C C C TS X-XI E = -1035.07345 DG = -1034.81165 C C C C C C C O -3.129480 0.499457 1.023593 -2.759025 -0.282798 -0.076843 -3.724062 -0.519869 -1.065886 -5.004074 0.016238 -0.976948 -5.361245 0.797312 0.124532 -4.418640 1.030070 1.122095 -1.380367 -0.913345 -0.288743 -1.407033 -2.060578 -0.828936 S10 3.234946 2.749166 3.621635 4.927775 5.403917 4.550647 1.351486 1.414409 0.630445 0.039100 0.317091 -0.938234 -1.342764 -1.889748 -3.213586 -4.017452 -3.477530 -1.226172 0.068494 1.017937 0.687357 -0.610077 -1.564035 0.524548 1.518730 -0.729824 -0.997726 0.477228 1.323846 -1.539532 -2.050639 -2.474791 -2.418557 -1.933457 -0.463869 -0.274601 0.274345 0.619896 0.411486 -0.134595 -0.714200 -1.553706 -1.269131 -0.015802 0.535390 0.280667 -0.043793 1.142234 1.199261 0.059704 -1.131557 C O H H H H H H H H H H H C C C C C H H H H H -2.155887 0.783452 0.671263 -1.737726 -4.092808 -5.050711 -3.619021 -1.261758 3.261889 5.583567 6.428565 4.907891 2.567364 -1.732623 -2.941586 -3.382273 -2.596693 -1.398815 -1.367834 -3.538795 -4.320776 -2.922894 -0.786092 -1.494462 0.586777 -1.660827 -1.099222 -1.894074 -2.757010 -2.859013 -2.101626 2.034882 1.443693 -0.869052 -2.578318 -1.972016 1.660798 2.340563 2.726718 2.415778 1.716351 1.369075 2.574973 3.265654 2.717429 1.478968 -1.181056 1.781808 0.610571 -2.104008 -2.029037 0.098194 2.133756 2.032688 0.424671 1.048981 0.671672 -0.308329 -0.891056 1.383344 1.241624 -0.024069 -1.133714 -0.985195 2.366782 2.122357 -0.143323 -2.128891 -1.849790 C C C C C H H H H H C C C C C H H H H H 4.192712 5.237084 5.013308 3.683537 2.622644 4.384289 6.255112 5.841431 3.484509 1.608006 -1.702965 -1.956766 -1.317954 -0.423728 -0.172696 -2.200121 -2.651250 -1.510558 0.087119 0.537981 0.196918 -0.476930 -1.624276 -2.068724 -1.410456 1.081047 -0.112945 -2.150617 -2.953237 -1.780067 2.787777 3.723499 3.620635 2.575988 1.637245 2.872622 4.539887 4.353588 2.490328 0.830845 -0.625152 -0.025891 0.766530 0.931722 0.341563 -1.231226 -0.169212 1.236215 1.537888 0.480930 -0.261151 0.73662 1.973677 2.194440 1.193662 -1.227414 0.548027 2.754054 3.151754 1.368711 3ag E = -1035.07860 DG = -1034.82244 C O C C C C H O C C C C C C H H H H H O S11 1.783794 0.531324 2.833259 -0.600803 -1.857521 -0.815273 -0.439389 -2.562797 -2.268742 -1.546020 -2.014726 -3.219242 -3.941063 -3.488125 -0.599549 -1.430544 -3.578349 -4.876666 -4.062718 1.894773 0.476576 -0.107788 -0.239188 0.715899 -0.119921 1.726743 1.271166 0.229795 -1.160389 -1.568935 -2.575075 -3.247941 -2.871784 -1.864657 -1.088920 -2.851043 -4.039336 -3.379089 -1.583890 1.515697 -1.095854 -0.901044 -0.464833 -1.152777 -1.403326 -0.044554 -2.086357 -2.416952 -0.509269 0.656454 1.482849 1.209687 0.065627 -0.768549 0.889881 2.361130 1.864204 -0.171895 -1.648680 -1.790361 Structures of Figure 7 E = -1242.08945 DG = -1242.86994 1a C C C C C C C O C O C C C C C C C S C O H H H H H H H H H H H H H H H E = -689.52009 DG = -689.36163 C O C C C C C C H H H H H C O C C C C C C H H H H H -0.869134 -0.178820 -1.618840 -1.501431 -2.224561 -3.073952 -3.200343 -2.472546 -0.838599 -2.132421 -3.641289 -3.863429 -2.571684 -0.863178 -0.161403 -1.616251 -1.488841 -2.214769 -3.076894 -3.213232 -2.482708 -0.816132 -2.114918 -3.646402 -3.886200 -2.589670 -0.494387 -1.497332 -0.140468 -0.953149 -0.652129 0.456405 1.264835 0.969758 -1.814192 -1.278383 0.690533 2.125341 1.606113 0.480174 1.475086 0.134938 0.946211 0.653563 -0.445089 -1.252009 -0.965357 1.799544 1.278714 -0.672649 -2.104801 -1.600527 0.135581 0.254307 -1.078278 -2.213748 -3.358148 -3.373052 -2.245204 -1.098126 -2.178853 -4.241388 -4.270453 -2.260632 -0.220787 1.314430 1.195310 2.528705 3.664103 4.808904 4.824285 3.696514 2.549033 3.628837 5.692088 5.722001 3.712314 1.671753 A 2.644689 1.794993 2.367569 3.740083 4.571775 4.016091 0.322696 -0.032105 -0.688136 -0.430573 -2.139565 -3.053981 -4.415342 -4.884951 -3.983132 -2.621969 0.112421 0.729345 1.168002 -0.480674 2.199400 4.651629 5.642917 4.161323 1.728688 -2.680270 -5.107735 -5.947354 -4.344554 -1.932847 0.873773 -0.826885 1.518612 1.962122 0.271013 -0.647187 -0.918882 -1.428634 -1.653789 -1.373864 -0.865726 -0.649020 -0.293977 -1.056588 -1.798205 -0.788905 -1.770931 -1.634402 -0.499991 0.491444 0.349753 0.952797 2.323520 3.462675 2.984718 -0.255891 -0.639581 -1.550297 -2.052189 -1.657067 -2.651399 -2.414081 -0.384279 1.386570 1.137777 0.645531 1.255372 4.397156 3.014774 3.638495 1.413212 0.332925 -0.842519 -0.924062 0.158191 1.330599 0.560537 1.704732 -0.464783 -1.434276 -0.145262 -0.540634 -0.277942 0.378501 0.766077 0.512766 -0.991629 -0.033139 -1.384834 0.638416 2.324560 2.184323 0.088138 -1.844968 -1.688543 -1.058205 -0.588501 0.582490 1.268488 0.807681 -1.716114 -1.473480 -0.936365 -1.989370 -1.987745 E = -552.55401 DG = -552.51673 I(A) S -0.116880 O 0.153199 C 1.306603 C -1.379005 H 1.320864 H 2.220072 H 1.209585 H -2.346180 H -1.325445 0.155787 -0.414269 1.497517 0.355873 -0.836120 0.126744 -0.831504 0.192787 -1.793470 -0.399757 -0.272396 -0.082114 -0.998461 1.207457 -0.443998 -0.146471 -0.958661 1.285016 E = -1242.12891 DG = -1242.90585 C 0.615146 C 0.185170 C 0.482167 C 1.196475 C 1.628347 C 1.336109 C -0.631713 O -0.712369 TS reactants- I(A) S12 -1.685936 1.316199 -1.468723 0.003472 -2.425119 -0.965791 -3.575533 -0.634699 -3.781022 0.674742 -2.829367 1.651893 -0.222743 -0.375554 0.048520 -1.699873 C O C C C C C C C S O C H H H H H H H H H H H H H H H -0.022443 -0.715892 1.407096 2.155125 3.496318 4.110819 3.375328 2.031215 -2.026399 -3.210737 -4.253739 -4.030441 0.155490 1.421994 2.193004 1.673107 0.395180 1.448814 3.849829 5.161381 4.065909 1.655975 -2.442355 -2.025675 -4.855601 -4.413192 -3.305978 1.042699 1.814635 1.383596 0.796541 1.125174 2.032711 2.618838 2.298203 -0.456929 0.825724 0.090731 1.085728 -2.235080 -4.313151 -4.674330 -2.977594 -0.945446 2.747549 3.324308 2.282788 0.673015 0.109392 -1.388701 -0.499144 1.783120 0.127899 1.513985 H H H H H H H H H H H H H 0.253039 0.916345 -0.018653 -1.047829 -1.214047 -0.350943 0.677376 0.838218 0.243863 -0.326513 -1.178328 1.273172 -1.987022 -1.402772 0.932742 2.675908 2.088062 1.639229 1.355567 -0.481196 -2.022811 -1.726274 -0.160837 1.339827 1.109022 1.641015 1.971862 IIA E = -1242.11658 DG = -1242.89346 C C C C C C C H H H H H O C O C C C C C C H H H H H C H H S O C H H H TS1(A) E = -1242.11413 DG = -1242.89217 C C C C C C C C S C C C C C C C C O O O H H -0.561823 -0.285027 -0.877561 -1.734224 -2.013589 -1.425587 0.656397 2.087436 3.415089 3.057120 0.272439 -1.184002 -2.223000 -3.548187 -3.855605 -2.824963 -1.500472 1.118665 0.436508 4.664337 -0.691572 -3.052862 1.514487 1.393466 2.283366 3.282392 3.392521 2.502285 0.320222 0.750189 -0.506904 -0.934332 -1.115378 -1.423716 -0.965519 -1.264948 -2.017099 -2.480060 -2.191175 -2.043667 -0.139438 0.382934 -2.554117 -3.069151 -4.891373 -2.244015 0.560952 -4.346184 -0.908318 -1.463366 -1.977288 -0.373000 -2.002300 -0.675170 2.170123 -2.092914 -2.190146 3.973471 -1.274031 -2.689280 4.165393 1.152287 -1.643614 2.578017 2.756074 -0.103940 0.813042 1.929991 2.441135 1.347530 -1.185356 2.168516 1.373503 0.567825 3.804486 -1.664937 1.914960 3.159402 -0.014508 2.181292 2.054257 -1.361398 1.668367 1.229301 -0.135585 -1.029040 -0.567858 0.792841 1.692916 -0.624825 -0.333207 -0.134205 1.595355 -0.523930 -0.311101 -1.124820 -0.815111 0.317916 1.133938 0.814954 -0.383151 -1.927755 -0.027143 1.447488 2.019928 S13 0.250752 -1.179910 -1.449430 -2.743921 -3.790660 -3.529821 -2.232881 -0.627896 -2.938929 -4.802972 -4.340450 -2.027995 1.102917 0.666251 0.337032 -0.257847 -1.162999 -2.021483 -1.994241 -1.099640 -0.239077 -1.192720 -2.717453 -2.666544 -1.075153 0.451396 2.123395 2.295494 2.478287 3.393192 4.655066 2.922068 3.633984 3.007324 1.909101 -1.130025 -1.412031 -1.765616 -2.073502 -2.046761 -1.701177 -1.377859 -1.795785 -2.337015 -2.292848 -1.678207 -1.088971 -2.080451 0.332332 -0.328362 1.437466 1.986695 3.015263 3.502831 2.953674 1.931971 1.591441 3.435761 4.302770 3.319901 1.502330 0.706271 1.474378 1.111874 -0.571899 0.302283 -0.838350 -1.550296 0.125636 -1.245421 -0.597927 -0.209817 1.115762 1.522659 0.599769 -0.724335 -1.123741 1.831638 2.560318 0.912843 -1.450110 -2.152498 -0.415757 -0.630175 -1.848655 -0.228936 -1.138900 -0.753634 0.550906 1.470043 1.081368 -2.151929 -1.476788 0.852433 2.494132 1.808680 -0.508842 0.256527 -1.466760 -0.116366 -0.013655 1.616053 2.041374 2.129638 1.655377 O O C C S O C C C C C C C H H H H H H H H H H H H H H H TS2(A) E = -1242.09899 DG = -1242.87697 C C C C C C C C S C O C O C C C C C C O H H H H H H H H H H H H H H H 1.369350 0.128337 -0.361115 0.345983 1.577423 2.071579 -0.605704 -2.084082 -2.928516 -2.328477 -0.018974 -0.016592 -0.847302 1.161000 2.432143 3.521286 3.354536 2.090404 1.007800 -4.407930 0.021081 1.952960 4.204430 4.505881 2.572401 1.762025 3.018573 2.131132 -0.072762 -1.314035 -2.545721 -2.506090 -2.693153 -2.736938 -1.233091 2.012493 1.629239 2.454163 3.559466 3.906901 3.120957 0.487481 0.456151 -0.803342 -0.168042 -0.164377 -1.331540 -2.218374 -1.584918 -1.082415 -1.402183 -2.225562 -2.745401 -2.438593 -0.399949 -2.847139 -3.395245 -2.469900 -1.008960 -0.457810 1.439854 3.378727 4.770560 4.159335 2.223471 1.399342 0.190955 -0.836989 0.838522 -0.158808 0.930659 0.365823 -0.678466 -1.131181 -0.570104 0.470954 0.852943 0.830288 -0.289288 -1.874071 1.996219 1.262107 1.494011 0.390149 0.684010 -0.125639 -1.235627 -1.524805 -0.710949 -0.232925 -0.922687 -2.386258 -1.868674 0.118286 1.560957 1.765295 0.943535 -0.930582 -1.937880 -1.148294 0.500075 1.808165 -2.657430 -2.021383 -1.869513 2.039295 0.145416 0.595787 0.881390 -0.671859 -0.160471 0.326351 -0.154871 -0.368628 -0.123295 0.346311 0.559004 -1.343486 -0.349439 -0.736046 -0.291835 0.548603 0.925354 -1.535200 -2.546425 -1.326939 0.913576 1.925555 1.327004 1.490363 -2.287734 -1.511118 -0.620656 DMF E = -248.37578 DG = -248.303206 C -0.088010 0.178702 0.076812 O -0.086063 0.018952 1.295257 H 0.645549 0.834461 -0.429528 N -0.943573 -0.393269 -0.792522 C -0.863202 -0.140987 -2.216512 C -1.988168 -1.292837 -0.346679 H -1.797938 0.303010 -2.579844 H -0.041294 0.548488 -2.427092 H -0.687140 -1.076404 -2.761429 H -2.972151 -0.897994 -0.627153 H -1.862917 -2.277479 -0.813081 H -1.935625 -1.396828 0.738180 E = -1242.11389 DG = -1242.89445 3.926028 2.744429 2.815243 4.052038 5.226591 5.161244 1.448622 0.663620 -0.122681 0.071271 1.440910 2.597347 4.012646 -1.023548 -2.273273 -3.362169 -3.296588 -2.081261 -0.979531 1.962315 -2.370789 -4.290467 -4.155257 -1.989709 -0.059582 -0.970994 -1.494939 -0.944478 0.123617 0.635152 1.551440 1.993007 2.473454 0.884784 2.167248 Other Structures III(A) C C C C C C C 1.363121 0.410714 -0.930622 -1.296821 -1.363978 -1.687801 -1.779925 -1.278041 -2.110941 -3.486388 -4.002652 -3.191091 -2.920352 -0.211621 -1.672543 -4.131815 -5.069931 -3.645565 1.898862 4.100759 6.192296 6.074909 3.859206 -2.293104 -0.569334 -3.123992 -2.818354 -3.718565 0.170508 0.945040 -0.132678 0.261216 -0.733918 -1.001352 -1.026564 -1.566366 -0.718456 -0.880934 -0.118778 0.376240 0.178641 0.919388 S14 C (Scheme 1) F (Scheme 5) E = -247.83143 DG = -247.77322 E = -247.71468 DG = -247.65524 C 0.020165 0.072202 -0.068182 N 0.116198 0.348413 1.338567 C 1.420347 0.120210 1.924323 C -1.006929 0.805351 2.052647 O -0.809993 1.015696 3.282488 H 0.256232 -0.980385 -0.297585 H -1.006432 0.280059 -0.393927 H 0.710442 0.698054 -0.658206 H 1.735264 -0.929292 1.811656 H 2.190795 0.749781 1.451685 H 1.362098 0.364484 2.989994 247.714678 C -0.000105 0.079460 -0.077170 N 0.139157 0.343197 1.344975 C 1.456573 0.109132 1.935481 C -0.886069 0.776118 2.064813 O -0.976853 1.050810 3.240578 H 0.228418 -0.971222 -0.290270 H -1.026076 0.295015 -0.383540 H 0.688932 0.712877 -0.647802 H 1.741332 -0.940616 1.802422 H 2.201685 0.744469 1.443672 H 1.421192 0.345334 3.000300 V (Scheme 5) E = -689.63884 DG = -689.48333 C O C C C C C C H H H H H C O C C C C C C H H H H H -1.937592 -1.812954 -2.056161 -1.718255 -1.845261 -2.331249 -2.685489 -2.545950 -1.353347 -1.566221 -2.435107 -3.075239 -2.814318 -1.931763 -1.792794 -2.055095 -1.706194 -1.836351 -2.336604 -2.701833 -2.559205 -1.330126 -1.548596 -2.442969 -3.102715 -2.836260 -0.477647 -1.725659 0.002122 -0.903956 -0.566659 0.689209 1.596024 1.263842 -1.886503 -1.287015 0.956761 2.575631 1.981640 0.475771 1.722257 -0.002595 0.899525 0.563721 -0.686453 -1.589121 -1.258576 1.877793 1.280810 -0.952784 -2.564164 -1.973231 0.173333 0.364292 -1.235804 -2.256781 -3.599303 -3.963280 -2.964648 -1.619818 -1.966991 -4.366140 -5.012686 -3.235759 -0.851438 1.277266 1.086230 2.686472 3.707255 5.049850 5.414105 4.415674 3.070765 3.417256 5.816527 6.463569 4.687007 2.302538 S15 1 H (300 MHz) and 13C (75 MHz) spectra (CDCl3) of 3ba Cl Cl O O O Cl 3ba S16 1 H (300 MHz) and 13C (75 MHz) spectra (CDCl3) of 6 OH N Ph O 6 S17 1 H (300 MHz) and 13C (75 MHz) spectra (CDCl3) of 7 Ph O O N Ph 7 O S18 1 H (300 MHz) and 13C (75 MHz) spectra (CDCl3) of 8 Cl OH O Ph OH N 8 S19 1 H (300 MHz) and 13C (75 MHz) spectra (CDCl3) of 12 OH Ph N Ph O 12 S20 1 H (300 MHz) and 13C (75 MHz) spectra (CDCl3) of 13 OAc OAc Ph Ph 13 S21 References 1. Y. Zhao, N. E. Schultz and D. G. Truhlar, J. Chem. Theory Comput., 2006, 2, 364-382. 2. Gaussian 09, Revision D.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, . Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski and D. J. Fox, Gaussian, Inc., Wallingford CT, 2009. 3. J. Tomasi, B. Mennucci and R. Cammi, Chem. Rev., 2005, 105, 2999-3093. S22

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Cross-benzoin and Stetter-type reactions mediated by KOtBu-DMF via an electron-transfer process