Supporting Information. P,N Ligands. General Information:

Transcription

1 Supporting Information A Dynamic Kinetic C Cross Coupling for the Asymmetric Synthesis of Axially Chiral,N Ligands edro Ramírez-López, Abel Ros, *, Beatriz Estepa, Rosario Fernández, *, Béla Fiser, Enrique Gómez-Bengoa,*, José M. Lassaletta*, Instituto Investigaciones Químicas (CSIC-US), C/ Américo Vespucio, 49, Sevilla, Spain. Departamento de Química Orgánica, C/ rof. García González, 1, Sevilla, Spain Departamento de Química Orgánica I, Universidad del aís Vasco, UV/EHU, Apdo. 1072, San Sebastián, Spain E mail: abel.ros@iiq.csic.es, jmlassa@iiq.csic.es, ffernan@us.es, enrique.gomez@ehu.es General Information: S2 Figure S1. Computed palladacycle int1-type intermediates (Figure 1 of the main text) at the B3LY/6-31G** (LANL2DZ for d anf Fe) level of theory. S 3 Figure S2. 2D and 3D representation of the pseudo-tetrahedral isomeric S-int1-L12 and S-int1-L12-c : S4 Figure S3. Computed transition-like structures TS2-type (Figure 3 of the main text) at the B3LY/6-31G** (LANL2DZ for d anf Fe) level of theory S6 Table S1. Energies of the structures involved in the computational study. Cartesian coordinates of the computed structures : References S7 S8-S60 S60 S1

2 General Information. All reported structures were optimized at DFT level by using the B3LY 1 hybrid functional as implemented in Gaussian Optimizations were carried out by using the standard 6-31G(d,p) basis set for C, H, O, N, S, F and. The LANL2DZ basis set, which includes the relativistic effective core potential (EC) of Hay and Wadt and employs a split-valence (double-z) basis set was used for d and Fe. 3 Reported energy values correspond to Gibbs Free (G) energies. The critical stationary points were characterized by frequency calculations in order to verify that they have the right number of imaginary frequencies, and the intrinsic reaction coordinates (IRC) 4 were followed to verify the energy profiles connecting the key transition structures to the correct associated local minima. The crucial structures shown in Figure 2 and Figure 3 of the main Text were single-poimt recalculated at M06/631+G(d,p)(LANL2DZ for d and Fe) (iefpcm,solvent=thf) level of theory. S2

3 Figure S1. Computed palladacycle int1-type intermediates (Figure 1 of the main text) at the B3LY/6-31G** (LANL2DZ for d anf Fe) level of theory. + + d N Fe d N Fe S-int1-L12 Structures in Figure 2 of the manuscript R-int1-L12 ΔG = +3.9 ΔG = N d Fe N d Fe S-int1-L12-b R-int1-L12-b ΔG = +5.3 ΔG = d N Fe d N Fe S-int1-L12-c R-int1-L12-c ΔG = +7.0 ΔG = N d Fe N d Fe S-int1-L12-d R-int1-L12-d ΔG = ΔG = S3

4 The palladium (II) center is severely distorted from the typical square planar geometry towards a pseudo-tetrahedral structure in int1-type species. This is the reason for the differentiation of the complexes depicted in Figure S1 in isomeric couples (like S-int1-L12 and S-int1-L12-c, see figure S2), which would correspond to a single isomer in the case of a square planar geometry. Figure S2. 2D and 3D representation of the pseudo-tetrahedral isomeric S-int1-L12 and S- int1-l12-c + + d N Fe d N Fe S-int1-L12 ΔG = +3.9 S-int1-L12-c ΔG = +7.0 As mentioned in the manuscript, for the calculation of the transmetalation transition states, we envisioned a model consisting in the approach of a molecule of h3 with simultaneous decoordination of the nitrogen atom of the isoquinoline ring. The location of the transition states with the full chiral L12 system proved difficult, and initially we could only get appropiate transition structures of complexes containing two H3 ligands instead of diphosphine L12. These structures showed h3 d distances ranging from 3.1 Å to 3.5 Å. We also scanned the energy of the incoming triphenylphosphine at different distances in TS-like structures, i.e. S-int1-L12, R-int1-L12, and others, showing that the maximum energy was obtained at an average distance of 3.35 Å. We thus took this value as the standard -d distance during the transition state, and computed all possible trajectories of h3 to build the following Figure S3. Noteworthy, the N-d distance was computed to be greater than 3.4 Å, indicating a complete decoordination of the nitrogen prior to S4

5 coordination of the phosphorous. In all cases, the imaginary frequencies of the transition structures are low, ranging from ca. 14 to 35, but they undoubtedly correspond to the forming -d bond vibration. S5

6 Figure S3. Computed transition-like structures TS2-type (Figure 3 of the main text) at the B3LY/6-31G** (LANL2DZ for d anf Fe) level of theory d N Fe + d N Fe + S-TS2-a ΔΔG = 0 R-TS2-a ΔΔG = +3.5 d N Fe + d N Fe + S-TS2-b ΔΔG = R-TS2-b ΔΔG = d Fe d Fe N N S-TS2-c ΔΔG = R-TS2-c ΔΔG = d Fe d Fe N N S-TS2-d ΔΔG = +9.8 R-TS2-d ΔΔG = S6

7 Table S1. Energies of the structures involved in the computational study. B3LY/6-31G** Electronic energy Correction to G B3LY/6-31G** Free Gibbs energy relative G Frequency Structures in Scheme 8 R-1A TS rot-1a-syn TS rot-1a-anti R-int1-Me TS rot-int Structures in Figure 2 and Figure S1 S-int1-L R-int1-L S-int1-L12-b R-int1-L12-b S-int1-L12-c R-int1-L12-c S-int1-L12-d R-int1-L12-d Structures in Figure 3 and Figure S3 S-TS2-a R-TS2-a S-TS2-b R-TS2-b S-TS2-c R-TS2-c S-TS2-d R-TS2-d Structures in Scheme 10 int TS Structures in Figure 4 int1-me Int S7

8 Cartesian coordinates of the computed structures R-1A Standard orientation: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S8

9 TS rot-1a Standard orientation: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S9

10 R-int1-Me 3 Standard orientation: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S10

11 TS rot-int1 Standard orientation: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S11

12 S-int1-L12 Standard orientation: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S12

13 S13

14 S14

15 R-int1-L12 Standard orientation: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S15

16 S16

17 S-int1-L12-b Standard orientation: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S17

18 S18

19 S19

20 R-int1-L12-b Standard orientation: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S20

21 S21

22 S-int1-L12-c Standard orientation: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S22

23 S23

24 S24

25 R-int1-L12-c Standard orientation: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S25

26 S26

27 S-int1-L12-d Standard orientation: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S27

28 S28

29 S29

30 R-int1-L12-d Standard orientation: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S30

31 S31

32 S-TS2-a Standard orientation: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S32

33 S33

34 S34

35 S35

36 R-TS2-a Standard orientation: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S36

37 S37