10.1002/chem.201703194
Chemistry - A European Journal
2
3
1H), 3.36 (dd, JH,H = 10.4 Hz, JH,H = 4.4 Hz, 1H), 3.52-3.63 (m, 3H), 3.98 (m, 1H),
4.87 (s, 1H), 5.10 (s, 1H), 7.34 (d, 3JH,H = 8.4 Hz, 2H), 7.38 (d, 3JH,H = 8.4 Hz, 2H), 7.68
Experimental procedures for the synthesis of the substrates and full spectroscopic data
for all new co mpounds and intermediates. Gibbs energy profiles for all possible
pathways not included in the main paper. Cartesian coordinates of all reactants,
intermediates, transition states, and products ofthe reaction.
(d, JH,H = 8.4 Hz, 2H), 7.72 (d, JH,H = 8.4 Hz, 2H); 13C-NMR (100 MHz, CDCl3,
TMS): δ(ppm) 13.0, 21.6, 21.8, 29.7, 38.9, 39.8, 43.5, 51.4, 52.5, 53.2, 111.8, 127.1,
127.7, 130.8, 132.6, 133.6, 133.8, 138.3, 143.9, 144.2; HRMS calcd. For [C27H32N2O4S2
+ Na]+: 535.1696. Found: 535.1675.
3
3
Acknowledgements
Cycloadduct 4d: was obtained as an inseparable mixture o f the two diastereoisomers
3
syn and anti. 1H-NMR (400 MHz, CDCl3, TMS, syn): δ(ppm) 0.90 (d, JH,H = 6.8 Hz,
3
Financial support fro m the Spanish Ministry of Education and Science (MINECO)
(Project No. CTQ2014-54306-P and CTQ2015-64436-P), the DIUE of the Generalitat
de Catalunya (Project No.: 2014SGR931, pre-doctoral grant to D.C. and ICREA
Academia 2014 prize to MS), and the FEDER fund (European Fund for Regional
Development) for grant UNGI08-4E-801 is gratefully acknowledged. The excellent
service by the Centre de Serveis Científics i Acadèmics de Catalunya (CESCA) is
gratefully acknowledged. We want to thank Dr. Ana Caballero and Prof. Pedro J. Pérez
for helpful discussion.
3H), 0.95 (d, JH,H = 6.8 Hz, 3H), 1.63 (m, 1H), 1.75 (m, 1H), 2.35-2.45 (m, 1H + 1H),
2
3
2.42 (s, 3H), 2.48 (s, 3H), 2.71 (dd, JH,H = 11.6 Hz, JH,H = 9.6 Hz, 1H), 2.98 (m, 1H),
2
2
3
3.26 (d, JH,H = 10.4 Hz, 1H), 3.38 (dd, JH,H = 10.4 Hz, JH,H = 4.8 Hz, 1H), 3.54-3.60
(m, 1H + 1H + 1H), 3.95 (m, 1H), 5.19 (d, JH,H = 10.4 Hz, 1H), 5.76 (d, JH,H = 2.4 Hz,
3
3
3
3
3
1H) 7.32 (d, JH,H = 8.4 Hz, 2H), 7.38 (d, JH,H = 8.4 Hz, 2H), 7.66 (d, JH,H = 8.4 Hz,
2H), 7.72 (d, 3JH,H = 8.4 Hz, 2H); 13C-NMR (100 MHz, CDCl3, TMS, syn): δ(ppm) 21.6,
23.0, 23.3, 27.6, 38.1, 38.5, 39.9, 50.0, 50.8, 52.3, 53.2, 122.2, 127.1, 127.6, 128.2,
129.8, 129.9, 132.7, 133.7, 134.5, 140.0, 143.8, 144.3; HRMS calcd. For [C28H34N2O4S2
+ Na]+: 549.1858. Found: 549.1855.
Abstract in Catalan: S’han preparat satisfactòriament una sèrie
de substrats de cadena oberta contenint un al.lè, un doble enllaç i un
alquí 3a-3h i s’ha evaluat la seva reacció de cicloaddició [2+2+2]
catalitzada per rodi. La cicloaddició és quimioselectiva degut a que
només el doble enllaç intern de l’al.lè reacciona per donar un
sistema tricíclic fusionat amb un doble enllaç exocíclic.
L’estereoselectivitat del procés depen del sistema catalític emprat.
La diferent reactivitat entre l’al.lè, l’alquè i l’alquí s’ha estudiat per
primer cop mitjançant càlculs teòrics basats en la teoria del
funcional de la densitat. Aquest estudi mecanístic determina l’ordre
en què les insaturacions participen en el cicle catalític.
Cycloadduct 4e: was obtained as an inseparable mixture of the two diastereoisomers
syn and anti. 1H-NMR (300 MHz, CDCl3, TMS): δ(ppm) 1.28 (m, 1Hanti), 1.82-1.88 (m,
2Hsyn), 2.38 (m, 1Hanti), 2.42-2.48 (m, 1Hsyn + 2Hanti), 2.44 (s, 3Hsyn + 3Hanti), 2.50 (s,
3Hsyn + 3Hanti), 2.77-2.94 (m, 2Hsyn + 1Hanti), 3.01 (m, 1Hanti), 3.14 (m, 1Hanti), 3.27-
2
3.38 (m, 2Hsyn), 3.59-3.78 (m, 3Hsyn + 4Hanti), 4.04 (d, JH,H = 15.0 Hz, 1Hsyn), 4.13 (d,
2JH,H = 15.3 Hz, 1Hanti), 5.97 (s, 1Hsyn), 6.03 (s, 1Hanti), 6.38 (s, 1Hsyn), 6.41 (s, 1Hanti),
7.13-7.38 (m, 9Hsyn + 9Hanti), 7.54-7.75 (m, 4Hsyn + 4Hanti); 13C-NMR (75 MHz, CDCl3,
TMS): δ(ppm) 21.6, 38.4, 38.7, 40.3, 42.5, 50.7, 51.0, 52.4, 122.8, 125.1, 127.2, 127.5,
127.7, 128.2, 128.6, 128.8, 129.8, 131.3, 132.6, 132.8, 133.4, 134.9, 136.8, 136.9, 143.9,
144.3; HRMS calcd. For [C31H32N2O4S2 + Na]+: 583.1701. Found: 583.1697.
Cycloadduct 4g: was obtained as an inseparable mixture o f the two diastereoisomers
syn and anti. 1H-NMR (400 MHz, CDCl3, TMS): δ(ppm) 0.86-0.97 (m, 6Hsyn + 3Hsyn
+
6Hanti + 3Hanti), 1.47 (m, 1Hanti), 1.67-1.74 (m, 2Hsyn), 1.90 (m, 1Hsyn), 1.98-2.05 (m,
2Hsyn), 2.07-2.11 (m, 2Hanti), 2.30 (m, 1Hanti), 2.35-2.43 (m, 1Hsyn + 2Hanti), 2.43 (s,
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For selected and recent reviews, see: a) A. Thakur, J. Louie, Acc. Chem. Res.
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Satoh, Y. Obora, Y. Eur. J. Org. Chem. 2015, 5041; d) D. L. J. Broere, E.
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2
6Hsyn + 6Hanti), 2.70 (dd, 2JH,H = 11.6 Hz, 3 JH,H = 10.0 Hz, 1Hanti), 2.82 (dd, JH,H = 10.8
3
2
Hz, JH,H = 9.6 Hz, 1Hsyn), 3.01 (m, 1Hanti), 3.01 (m, 1Hanti), 3.15 (dd, JH,H = 10.8 Hz,
3JH,H = 9.2 Hz, 1Hsyn), 3.21 (d, JH,H = 10.8 Hz, 1Hanti), 3.70 (dd, 2JH,H = 10.4 Hz, JH,H
4.4 Hz, 1Hsyn), 3.46 (dd, JH,H = 9.2 Hz, JH,H = 7.2 Hz, 1Hsyn), 3.51-3.74 (m, 6Hsyn
6Hanti), 3.94-4.12 (m, 1Hsyn + 1Hanti), 5.30 (dd, JH,H = 10.4 Hz, JH,H = 2.4 Hz, 1Hsyn),
5.34 (d, JH,H = 10.0 Hz, 1Hanti), 7.32-7.39 (m, 4Hsyn + 4Hanti), 7.68-7.72 (m, 4Hsyn
=
+
3
4
2
3
2
3
2
+
4Hanti); 13C-NMR (100 MHz, CDCl3, TMS): δ(ppm) 13.3, 21.6, 21.9, 23.1, 23.2, 23.5,
23.9, 27.8, 28.1, 38.4, 38.9, 40.0, 43.2, 43.8, 45.5, 50.3, 50.4, 52.3, 53.5, 126.8, 127.2,
127.4, 127.8, 129.8, 129.9, 130.0, 130.9, 131.3, 132.6, 133.9, 134.6, 143.7, 143.9, 144.0
144.3; HRMS calcd. For [C30H38N2O4S2 + Na]+: 577.2171. Found: 577.2171.
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Cycloadduct 4h: was obtained as an inseparable mixture o f the two diastereoisomers
syn and anti. 1H-NMR (400 MHz, toluene-D8, TMS): δ(ppm) 1.53 (m, 1Hsyn), 1.81 (m,
1Hanti), 1.95-1.99 (m, 2Hsyn + 2Hanti), 1.95 (s, 3Hsyn + 3Hanti), 2.39 (m, 1Hsyn), 2.63 (dd,
3
2JH,H = 10.4 Hz, 3JH,H = 9.2 Hz, 1Hanti), 2.72 (dd, 2JH,H = 10.4 Hz, JH,H = 8.0 Hz, 1Hanti),
2
3
2.78-2.82 (m, 1Hsyn + 1Hanti), 3.04 (m, 1Hsyn), 3.35 (dd, JH,H = 9.2 Hz, JH,H = 7.2 Hz,
2
1Hanti), 3.50 (t, JH,H = 9.5 Hz, 1Hanti), 3.67-3.78 (m, 1Hsyn + 3Hanti), 3.89-3.96 (m,
For selected reviews on the use of allenes as substrates in cycloaddition and
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989; b) M. E. Muratore, A. Ho ms, C. Obradors, A. M. Echevarren, Chem. Asian
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2Hsyn), 4.08 (d, 3JH,H = 14.8 Hz, 1Hanti), 4.18 (d, 3JH,H = 14.0 Hz, 1Hsyn), 4.42 (s, 1Hsyn),
3
4.62 (s, 1Hanti), 4.74 (s, 1Hsyn), 5.49 (s, 1Hanti), 6.80 (d, JH,H = 8.0 Hz, 2Hsyn), 6.84 (d,
3
3JH,H = 8.0 Hz, 2Hanti), 7.64 (d, 3JH,H = 8.0 Hz, 2Hsyn), 7.72 (d, JH,H = 8.0 Hz, 2Hanti);
13C-NMR (100 MHz, toluene-D8, TMS): δ(ppm) 13.7, 41.4, 42.1, 45.9, 48.9, 50.4, 51.6,
51.9, 60.9, 107.5, 113.1, 115.7, 129.4, 129.5, 130.2, 134.3, 136.0, 142.5, 143.5, 144.5,
144.5; HRMS calcd. For [C18H21NO3S + Na]+: 354.1140. Found: 354.1134.
Computational details: All geometry optimisations were performed without symmetry
constraints using the hybrid DFT B3LYP [18] method with the all-electron cc-pVDZ basis
set for P, Cl, O, C, and H[19] and the cc-pVDZ-PP basis set containing an effective core
relativistic pseudopotential for Rh.[20] The D3 Grimme energy corrections for dispersion
with its original damping function[21] were added in all B3LYP/cc-pVDZ-PP
calculations. Analytical Hessians were computed at the B3LYP-D3/cc-pVDZ level of
theory to determine the nature of stationary points (one or zero imaginary frequencies
for transition states and minima, respectively) and to calculate unscaled zero -point
energies (ZPEs) as well as thermal corrections and entropy effects by using the standard
statistical-mechanics relationships for an ideal gas.[22] These last two terms were
computed at 373.15 K (for the [RhCl(PPh3)3] cycle) or 333.15 K (for the [RhCl(CO)2]2
cycle) and 1 atm to provide the reported relative Gibbs energies. Furthermore, the
connectivity between stationary points was established by intrinsic reaction path
calculations.[23] All calculations were performed with the Gaussian 09[24] program
package. Previous studies found that solvent effects due to toluene in [2+2+2]
cycloadditions are minor, likely due to the absence of charged or polarized
intermediates and transition states in the reaction mechanism.[10a][25] Because the
reactions studied are carried out in toluene solution, solvent effects have not been
included in the present calculations.
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Supporting Information
9
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