Theoretical study of the BF 3-promoted rearrangement of oxiranyl N-methyliminodiacetic acid boronates
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1 Theoretical study of the BF 3-promoted rearrangement of oxiranyl N-methyliminodiacetic acid boronates Margarita M. Vallejos a* and Silvina C. Pellegrinet b* a Laboratorio de Química Orgánica, IQUIBA-NEA, Universidad Nacional del Nordeste, CONICET, FACENA, Av. Libertad 5460, Corrientes 3400, Argentina. vallejos.marga@gmail.com b Instituto de Química Rosario (CONICET), Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario, Suipacha 531, Rosario 2000, Argentina. pellegrinet@iquir-conicet.gov.ar Supporting Information List of contents Computational methods. Page S3. Optimized geometries of reactive-complexes and TSs involved in the mechanisms of 2- phenyl oxiranyl MIDA boronate (1) with selected bond distances, Wiberg bond indices (WBIs) and dihedral angles (Figure S1). Pages S4 and S5. Bond distances and Wiberg bond indices (WBIs) for reactive-complexes and TSs involved in the mechanisms of 2-phenyl oxiranyl MIDA boronate (1) (Table S1). Page S6. Natural atomic charges for reactive-complexes and TSs involved in the mechanisms of 2- phenyl oxiranyl MIDA boronate (1) (Table S2). Page S6. Optimized geometries of reactive-complexes and TSs involved in the mechanisms of 1- phenyl oxiranyl MIDA boronate (24) with rupture of the C1-O bond with selected dihedral angles (Figure S2). Page S7. Bond distances and Wiberg bond indices (WBIs) for reactive-complexes and TSs involved in the mechanism of 1-phenyl oxiranyl MIDA boronate (24) with rupture of the C1-O bond (Table S3). Page S8. Natural atomic charges for reactive-complexes and TSs involved in the mechanisms of 1- phenyl oxiranyl MIDA boronate (24) with rupture of the C1-O bond (Table S4). Page S8. Reaction pathways of the rearrangement of the complex 1-phenyl oxiranyl MIDA boronate- BF 3, with rupture of the C2-O (Figure S3) and corresponding discussion. Pages S9 and S10. Optimized geometries of reactive-complexes and TSs involved in the mechanisms of 1- phenyl oxiranyl MIDA boronate (24), with rupture of the C1-O bond with selected bond distances, Wiberg bond indices (WBIs) and dihedral angles (Figure S4). Page S11. Bond distances and Wiberg bond indices (WBIs) for reactive-complexes and TSs involved in the mechanisms of 1-phenyl oxiranyl MIDA boronate (24) with rupture of the C2-O bond (Table S5). Page S11. S1
2 Natural atomic charges for reactive-complexes and TSs involved in the mechanisms of 1- phenyl oxiranyl MIDA boronate (24) with rupture of the C2-O bond (Table S6). Page S11. Optimized geometries of reactive-complexes and TSs involved in the mechanisms of oxiranyl MIDA boronate (31) with selected bond distances, Wiberg bond indices (WBIs) and dihedral angles (Figure S5). Page S12. Bond distances, and Wiberg bond indices (WBIs) for reactive-complexes and TSs involved in the mechanis of oxiranyl MIDA boronate (31) (Table S7). Page S13. Natural atomic charges for reactive-complexes and TSs involved in the mechanisms of oxiranyl MIDA boronate (31) (Table S8). Page S13. MPWB1K /6-311G* Cartesian coordinates, absolute electronic energies (including zeropoint energy -ZPE- corrections) and free energies in DCM of the stationary points. Imaginary frequencies of transition structures. Pages S14-S40. References. Page S41. S2
3 Computational methods We initially performed thorough conformational searches to locate the lowest energy geometries of the chemical species under study. Final geometry optimizations were carried out using the MPWB1K 1 global hybrid meta-gga functional together with the 6-311G* basis set. Frequency calculations were performed to determine the nature of the stationary points: the transition structures (TSs) had one imaginary frequency and the reactants, the intermediate structures and the products had no imaginary frequencies. Solvent effects in DCM (solvent used experimentally) were taken into account through full optimizations using the SMD continuum solvation method. 2 Free energies were computed at K and 1 atm in DCM. To verify the connectivity of the TSs with the correct local minima, intrinsic reaction coordinates (IRCs) were computed from every optimized TS in forward and reverse directions along the imaginary mode of vibration using either the Hessian-based predictor corrector (HPC) 3-4 or the local quadratic approximation (LQA) 5-6 algorithms. Bond orders (Wiberg Bond indices, WBIs) 7 and atomic charges were calculated with the natural bond orbital (NBO) 8-9 method. All computations were carried out with the Gaussian 09 suite of programs. 10 S3
4 Rearrangement of the complex 2-phenyl-oxiranyl MIDA boronate-bf 3 Figure S1. Optimized geometries of reactive-complexes and TSs involved in the mechanisms of 2-phenyl oxiranyl MIDA boronate (1) with selected bond distances (in Å), Wiberg bond indices (WBIs, in italics) and dihedral angles. S4
5 Figure S1. Continued. S5
6 Table S1. Bond distances (in Å) and Wiberg bond indices (WBIs, in italics) for reactivecomplexes and TSs involved in the mechanisms of 2-phenyl oxiranyl MIDA boronate (1). Specie C1-O C2-O C1-C2 C1-B C1-H a C2-H b C2-C3 O-B(F 3) trans-1-bf cis-1-bf Table S2. Natural atomic charges (in e) for reactive-complexes and TSs involved in the mechanisms of 2-phenyl oxiranyl MIDA boronate (1). Species C1 C2 O C3 B H a H b B(F 3) trans-1-bf cis-1-bf S6
7 Rearrangement of the complex 1-phenyl-oxiranyl MIDA boronate-bf3 Rupture of the C1-O bond Figure S2. Optimized geometries of reactive-complexes and TSs involved in the mechanisms of 1-phenyl oxiranyl MIDA boronate (24) with rupture of the C1-O bond with selected dihedral angles. S7
8 Table S3. Bond distances (in Å) and Wiberg bond indices (WBIs, in italics) for reactivecomplexes and TSs involved in the mechanism of 1-phenyl oxiranyl MIDA boronate (24), with rupture of the C1-O bond. Specie C1-O C2-O C1-C2 C1-B C2-H a C2-H b C1-C3 O-B(F 3) C1-H a trans-24-bf cis-24-bf Table S4. Natural atomic charges (in e) for reactive-complexes and TSs involved in the mechanisms of 1-phenyl oxiranyl MIDA boronate (24) with rupture of the C1-O bond. Species C1 C2 O C3 B H a H b B(F 3) trans-24-bf cis-24-bf S8
9 Rupture of the C2-O bond. Figure S3. Reaction pathways of the rearrangement of the complex 1-phenyl oxiranyl MIDA boronate-bf 3 with rupture of the C2-O. Relative Gibbs free energies in DCM are given between parentheses (in kcal/mol). S9
10 The mechanism for the reaction of BF 3-coordinated 1-phenyl oxiranyl MIDA boronate (24) with ring opening at the less substituted bond (C2-O) is displayed in Figure S3. In Table S5 distances and WBIs for selected bonds of TSs are shown. Two routes can be followed in which the C-O bond is approaching to H b/h a, which we named anti/syn pathways. The concerted mechanisms from trans-24-bf 3 may occur via TSs S-1 and S-2 following anti and syn paths, respectively. Both pathways involve a BMIDA migration to lead compound 23 (-30.0 kcal/mol) which is also generated from cis-1-bf 3 (See Figure 3 in the manuscript). TS S-1 (44.8 kcal/mol) has higher energy than TS S-2 (32.5 kcal/mol). In TSs S-1, the phenyl is placed more favorably to migrate (C2-C1-C3= 118 ). However, the migration of the BMIDA group occurs while in TS S-2 the BMIDA group is placed more favorably to migrate toward C1. Cis-24-BF 3 may also undergo a one-step mechanism through the syn pathway with BMIDA shift via TS S-4. This route leads to S-7, which is the endo analogue of 23 (endo indicates that BF 3 is closer to C1-C2 bond), and has a lower energy (-34.7 kcal/mol). Cis-24-BF 3 may also undergo a stepwise mechanism through the anti-pathway via TS S-3, to generate the intermediate BF 2-bound fluorohydrin S-5. This mechanism involves a fluorine transfer from the BF 3 group to the carbocation at C2. In TS S-3 a fluorine atom of BF 3 group is in a favorable position to interact with C2 (C2-F = 2.25 Å and WBI = 0.113). In the second step of the mechanism, S-5 undergoes phenyl migration to yield 15-N through TS S N is also generated from trans-1-bf 3 (See Figure 2 in the manuscript). These mechanisms have much larger activation barriers than those associated with the rupture of the C1-O bond (See Figure 5 in the manuscript), which is mainly attributed to the lack of the resonance contribution. S10
11 Figure S4. Optimized geometries of reactive-complexes and TSs involved in the mechanisms of 1-phenyl oxiranyl MIDA boronate (24) with rupture of the C1-O bond. Selected bond distances in Å, Wiberg bond indices (WBIs, in italics) and dihedral angles are shown. Table S5. Bond distances in Å, and Wiberg bond indices (WBIs, in italics) for reactive-complexes and TSs involved in the mechanisms of 1-phenyl oxiranyl MIDA boronate (24) with rupture of the C2-O bond. Specie C1-O C2-O C1-C2 C1-B C2-H a C2-H b C1-C3 O-B(F 3) S S S S S Table S6. Natural atomic charges in e, for reactive-complexes and TSs involved in the mechanisms of 1-phenyl oxiranyl MIDA boronate (24) with rupture of the C2-O bond. Species C1 C2 O C3 B H a H b B(F 3) S S S S S S11
12 Rearrangement of BF3-coordinated oxiranyl MIDA boronate Figure S5. Optimized geometries of reactive-complexes and TSs involved in the mechanisms of oxiranyl MIDA boronate (31) with selected bond distances (in Å), Wiberg bond indices (WBIs, in italics) and dihedral angles. S12
13 Table S7. Bond distances in Å and Wiberg bond indices (WBIs, in italics) for reactive-complexes and TSs involved in the mechanis of oxiranyl MIDA boronate (31). Specie C1-O C2-O C1-C2 C1-B C1-H a C2-H b C2-H c O-B(F 3) trans-31-bf cis-31-bf Table S8. Natural atomic charges (in e) for reactive-complexes and TSs involved in the mechanisms of oxiranyl MIDA boronate (31). Species C1 C2 O B H a H b H c B(F 3) trans-31-bf cis-31-bf S13
14 MPWB1K /6-311G* Cartesian coordinates, absolute electronic energies (including zeropoint energy -ZPE- corrections) and free energies in DCM of the stationary points. Imaginary frequencies of transition structures. 1 C C C O O C C B O O C C N O C C C C C C H H H H H H H H H H H H H H au au. trans-1-bf 3 C C C O O C C B O O C C N O C C C C C C B F F F H H H H H H H H H H H H H H au au. cis-1-bf 3 C C C O O C S14
15 C B O O C C N O C C C C C C B F F F H H H H H H H H H H H H H H au au. 2 C C C O O C C B O O C C N O C C C C C C B F F F H H H H H H H H H H H H H H au au. 1 imaginary frequency : cm -1 3 C C C O O C C B O O C C N O C C C C C C B F F F S15
16 H H H H H H H H H H H H H H au au. 1 imaginary frequency : cm-1 4 C C C O O C C B O O C C N O C C C C C C B F F F H H H H H H H H H H H H H H au au. 1 imaginary frequency : cm-1 5 C C C O O C C B O O C C N O B F F F C C C C C C H H H H H H H H H H H H H H au. S16
17 au. 1 imaginary frequency : cm-1 6 C C C O O C C B O O C C N O C C C C C C B F F F H H H H H H H H H H H H H H au au. 7 C C C O O C C B O O C C N O C C C C C C B F F F H H H H H H H H H H H H H H au au. 8 C C O C C C C C C B S17
18 F F F H H H H H H H C C O O C C B O O C N H H H H H H H au au. 9 C C C O O C C B O O C C N O B F F F C C C C C C H H H H H H H H H H H H H H au au. 10 C C O C C C C C C B F F F H H H H H H H C C O O C C B O S18
19 O C N H H H H H H H au au. 1 imaginary frequency : cm-1 11 C C C O O C C B O O C C N O C C C C C C B F F F H H H H H H H H H H H H H H au au. 1 imaginary frequency : cm-1 12 C C C C O C C C C B F F F H H H H H H H C C O O C C B O O C N H H H H H H H au au. 1 imaginary frequency : cm-1 S19
20 13 C C C O O C C B O O C C N O B F F F C C C C C C H H H H H H H H H H H H H H au au. 1 imaginary frequency : cm-1 14-X C C C C O C C C C C C O O C C B O O C N B F F F H H H H H H H H H H H H H H au au. 14-N C C C C O C C C C C C O O C C S20
21 B O O C N B F F F H H H H H H H H H H H H H H au au. 15-N C C C O O C C B O O C C N O C C C C C C B F F F H H H H H H H H H H H H H H au au. 15-X C C C O O C C B O O C C N O B F F F C C C C C C H H H H H H H S21
22 H H H H H H H au au. 16 C C C O O C C B O O C C N O C C C C C C B F F F H H H H H H H H H H H H H H au au. 1 imaginary frequency : cm-1 17 C C C O O C C B O O C C N O C C C C C C B F F F H H H H H H H H H H H H H H au au. 1 imaginary frequency : cm-1 18 C C C S22
23 O O C C B O O C C N O C C B F F F C C C C H H H H H H H H H H H H H H au au. 1 imaginary frequency : cm-1 19 C C C O O C C B O O C C N O C C C C C C B F F F H H H H H H H H H H H H H H au au. 1 imaginary frequency : cm-1 20 C C C O O C C B O O C C N O C C C C C S23
24 C B F F F H H H H H H H H H H H H H H au au. 21 C C C O O C C B O O C C N O C C C C C C B F F F H H H H H H H H H H H H H H au au. 22 C C C O O C C B O O C C N O C C C C C C B F F F H H H H H H H H H H H H S24
25 H H au au. 1 imaginary frequency : cm-1 23 C C C O O C C B O O C C N O C C C C C C B F F F H H H H H H H H H H H H H H au au. 24 C C C O O C C B O O C C N C C O C C C C H H H H H H H H H H H H H H au au. trans-24-bf 3 C C C S25
26 O O C C B O O C C N C C O C C C C B F F F H H H H H H H H H H H H H H au au. cis-24-bf 3 B F F F C C C O O C C B O O C C N C C O C C C C H H H H H H H H H H H H H H au au. 25 C C C O O C S26
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