Electronic Supplementary Information for Origin of Stereoselectivity in the Amination of Alcohols

157 Pages·2017·2.47 MB·English

Electronic Supplementary Material (ESI) for Chemical Science.
This journal is © The Royal Society of Chemistry 2018
Electronic Supplementary Information
for
Origin of Stereoselectivity in the Amination of Alcohols using Cooperative Asymmetric
Dual Catalysis Involving Chiral Counter-ion

Soumi Tribedi,a Christopher M. Hadad,b and Raghavan B. Sunoj a,*
a Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076
b Department of Chemistry and Biochemistry, The Ohio State University, Columbus, OH
43210
S1
Page Table of Contents
No.
S4 Fig. S1 Model systems of the catalysts used in the preliminary mechanistic
investigation.
S4 Fig. S2 Natural population analysis of catalyst A .
model
S5 Fig. S3 Conformers and configurations of catalyst A .
model
S6 Fig. S4 The TS for concerted dehydrogenation of 1(2S,3S) by catalyst
B .
model
S6 Table S1 The relative free energies (kcal/mol) of the stereoisomers of the TS
for concerted dehydrogenation of 1(2S,3S) by catalyst B .
model
S7 Fig. S5 The TS for stepwise dehydrogenation of 1(2S,3S) by B .
model
S7 Table S2 The relative free energies (kcal/mol) of the stereoisomers of the TS
for the stepwise dehydrogenation of 1(2S,3S) by catalyst B .
model
S8 Fig. S6 The TS for concerted outer-sphere dehydrogenation of 1(2S,3S) by
catalyst C .
model
S8 Table S3 The relative free energies of the stereoisomers of the TS for
concerted outer-sphere dehydrogenation of 1(2S,3S) by catalyst
C .
model
S9 Fig. S7 Extended internal reaction coordinate for TS1 .
SS
S9 Fig. S8 The TS for concerted inner-sphere dehydrogenation of 1(2S,3S) by
catalyst C .
model
S9 Table S4 The relative free energies of the stereoisomers of the TS for
concerted inner-sphere dehydrogenation of 1(2S,3S) by catalyst
C .
model
S10 Fig. S9 The TS for concerted dehydrogenation of 1(2S,3S) by catalyst
D .
model
S10 Table S5 The relative free energies of the stereoisomers of the TS for
concerted dehydrogenation of 1(2S,3S) by catalyst D .
model
S11 Fig. S10 NCI plots for C and D.
S12 Scheme S1 Mechanism of condensation of ketone with aryl amine catalyzed by
A
S12 Fig. S11 The TSs for condensation of ketone catalyzed by phosphoric acid
S13 Fig. S12 General representation of different orientations of the TS for
dehydrogenation from 1(2X,3S), X being the configuration (S or R).
S14-S16 Table S6 Conformational analysis of concerted dehydrogenation of alcohols
1(2S,3S) and 1'(2R,3S) by ion-pair catalyst dyad C.
S16 Fig. S13 General representation of different orientations of the TS for
asymmetric hydride addition to (S)-iminium.
S2
S17-S20 Table S7 Conformational analysis of asymmetric hydride addition to (S)-
iminium to form 3(2S,3S) and 3'(2R,3S).
S20 Fig. S14 The TSs for asymmetric hydride addition to (S) and (R) iminium
S21 Fig. S15 The TSs for asymmetric hydride addition to (Z)-(S)-iminium and
(E)-(R)-iminium
S22 Fig. S16 The TSs for phosphoric acid catalysed epimerization of (R)-ketone
S23 Fig. S17 The TSs for phosphoric acid catalysed epimerization of (R)-
iminium
S24 Fig. S18 The relative free energy profile for epimerization of (R)-iminium
S24 Fig. S19 NCI plots for diastereomeric transition states TS2 and TS2
SS RS
with the interactions between substrate and catalyst dyad marked
explicitly.
S25 Fig. S20 Full mapping of noncovalent interactions of TS2 and TS2
SS RS
obtained using the AIM analysis.
S26 Table S8 The distances, angles and electron densities (ρ x 10-2 au) at the
bcps of the noncovalent contacts.
S27 Table S9 The relative free energies (in kcal/mol) of the important species
involved in asymmetric amination of alcohol through the most
favoured pathway
S28- Cartesian coordinates of the optimized geometries of various stationary points
S157 obtained at the M06 level of theory.
S3
1. Model Systems of the Catalysts Used in the Preliminary Mechanistic Investigations
A A
real model
B B
real model
Fig. S1 The model catalysts used for our preliminary mechanistic study wherein the phenyl
rings on the diamino backbone is replaced by methyl and pentamethyl aryl (C Me ) of the
6 5
‒NSO group is replaced by a phenyl ring. In the SPINOL phosphoric acid, the isopropyl
2
substituents are replaced by hydrogens.
2. Natural Population Analysis of A
model
atom (number) natural charge
Ir (1) 0.68
H (8, 56) 0.46
S (13) 2.41
N (7) -0.90
Fig. S2 The NPA charges on some important atoms of the cationic Ir complex. The chiral
phosphate was placed closer to the most positively charged centres in the cationic Ir
complex in the initial guess geometries. We noted that the counter ion invariably moved
closer to the ‒NH hydrogen atoms in the converged minimum energy geometry when the
2
phosphate oxygen atoms developed strong hydrogen bonding interaction.
S4
3. Conformers and Configurations of the Metal Catalyst A
model
1 Cp* 1 Cp*
PIHrhON2SN2MMH3eeH PhO2SN3 2NH PhO24SNMe3 Ir MN2eH2 P4hMOe2SN3 Ir 2NH2M1e PhO2SN3 2NH PhOIHr2SNN3HH2MM14ee
4  
δ
λ
Cp* H Cp* H
Me Me
Ir Ir Me Ir Me Ir
PhO2SN NH2 PhO2SN NH2 PhO2SN NH2 PhO2SN NH2
H *Cp H Me Cp* Me
Me Me
IrH(S, IrH(R, IrH(S, IrH(R,
1.2 0.0 9.8 3.1
Fig. S3 The δ and λ conformers of the five-membered chelate bound to the Ir center and the
four different stereoisomers of the corresponding [Ir]-H complex. The relative free energy
(kcal/mol) profile for the interconversion of λ (left) and δ (right) conformers.
4. Active Catalysts Considered for the Alcohol Dehydrogenation Step
The (2S,3S) stereoisomer of alcohol 1 is used as a representative case for the evaluation of
energetics using different possible catalyst complexes in the dehydrogenation step as
summarized below.
S5
Cp*
PhO S Ir
2 Me
N H
HN
Me Ph
H
O
OH H O
Me Me
Ph TS1 (31.5) Ph
Bcon
Me + B Me
Me Me
1(2S,3S) 1a(3S)
Fig. S4 The TS for concerted dehydrogenation of 1(2S,3S) by catalyst B . Relative free
model
energy (in kcal/mol) of the most favored conformer of the TS given in parentheses is at the
SMD /B3LYP-D3/6-31G**,SDD(Ir) Level of Theory. Distances are in Å.
(toluene)
Table S1. The Relative Free Energies (kcal/mol) of the Four Possible Stereoisomers of the
Transition States of Concerted Dehydrogenation of Alcohol by Metal Catalyst B at the
model
B3LYP-D3/6-31G**, SDD(Ir) Level of Theory
Chirality on the metal
Conformation of the five R S
membered chelate
δ 15.9 18.7
λ 16.2 8.3
S6
Cp* Cp*
PhO2S N Ir Me PhO2S N Ir O Ph
O Me
Me HN Ph H
H N H H
H 2 Me
OH Me H Me H Me Cp* Me Me Me Ph Cp*
Ph Me + B TS1Bstep1(10.6) MHe O IrN NH2MeTS1Bstep2(40.6) Me O NIr NHH
2
Me Ph PhO S
PhO S 2
1(2S,3S) 2 Me
Me Me
TS1 TS1
Bstep1 Bstep2
Fig. S5 The TS for stepwise dehydrogenation of 1(2S,3S) by catalyst B . Relative free
model
energy (in kcal/mol) of the most favored conformer of the TS given in parentheses is
obtained at the SMD /B3LYP-D3/6-31G**,SDD(Ir) Level of Theory. Distances are
(toluene)
given in Å.
Table S2. The Relative Free Energies (kcal/mol) of the Four Possible Stereoisomers of the
Transition States for the Stepwise Dehydrogenation of Alcohol by Metal Catalyst B at
model
the B3LYP-D3/6-31G**,SDD(Ir) Level of Theory
Chirality on the metal
Conformations of five R S
membered chelate
δ 7.3 4.9
λ 8.9 4.8
S7
*Cp H Me
N
O Ir Me
* O N
O P H SO Ph
2
H
O Me
O
H
OH Ph H O
Me
Ph TS1 (-3.4) Ph
Me + C SS Me
Me ActivationBarrier Me
1(2S,3S) =28.8kcal/mol 1a(3S)
Fig. S6 The TS for concerted outer-sphere dehydrogenation of 1(2S,3S) by catalyst C .
model
Relative free energy (in kcal/mol) of the most favored conformer of the TS given in
parentheses is obtained through reoptimization at the SMD /B3LYP-D3/6-
(toluene)
31G**,SDD(Ir) Level of Theory. Distances are given in Å.
Table S3. The Relative Free Energies (kcal/mol) of the Four Possible Stereoisomers of the
TS of Concerted Outer-sphere Dehydrogenation of Alcohol by Catalyst Dyad C at the
model
B3LYP-D3/6-31G**, SDD(Ir) Level of Theory[1]
Chirality on the metal
Conformations of five R S
membered chelate
δ -12.8 -13.3
λ -10.1 -13.3
[1] See Fig. 1 in main text for catalyst dyad C. A and B form similar complex C .
model model model
Based on the above free energies, the reaction is inferred to take place via concerted
dehydrogenation by the ion pair complex C . The concertedness of the process is verified
model
by extended reaction coordinate plot in Fig. S7.
S8
Fig. S7 Internal Reaction Coordinate extended up to 50 points for TS1 . The IRC plot
SS
suggests the absence of any intermediates between the TS and the two ends of the IRC that
connects to the reactant/products. Hence, the mechanism is a concerted process.
Cp* H Me
H N
O Ir Me
* O N
O P SO Ph
O H Me 2
O
OH Cp* N H Me H Me Ph H O
Ph * O O Ir N Me TS1inner Ph
Me + C O P H SO Ph Me
O 2
Me O H Me Me
1(2S,3S) Me H 1a(3S)
Ph
Fig. S8 The TS for concerted inner-sphere dehydrogenation of 1(2S,3S) by C . (The
model
inner-sphere TS was not optimised in SMD as the gas phase energies were too high compared
to the outer-sphere analogue.)
Table S4. The Relative Energies (kcal/mol) of the Four Possible Stereoisomers of the TS of
Concerted Inner-sphere Dehydrogenation of Alcohol by C at the B3LYP-D3/6-31G**,
model
SDD(Ir) Level of Theory
Chirality on the metal
Conformations of five R S
membered chelate
δ 25.4 24.2
λ 23.6 23.4
S9
Cp* H H
N Me
O Ir Me
* N
O P O SO Ph
2
H Me
O
O H
OH H O
Me Ph
Ph TS1 (35.5) Ph
Me + D Dcon Me
Me Me
1(2S,3S) 1a(3S)
Fig. S9 The TS for concerted dehydrogenation of 1(2S,3S) by catalyst dyad D . Relative
model
free energy given in parenthesis of the most favoured conformer of TS at the
SMD /B3LYP-D3/6-31G**,SDD(Ir) Level of Theory. Distances are given in Å.
(toluene)
Table S5. The Relative Energies (kcal/mol) of Two Stereoisomers of the TS of Concerted
Dehydrogenation of Alcohol by D at the B3LYP-D3/6-31G**, SDD(Ir) Level of
model
Theory[2]
Chirality on the metal
R S
32.0 20.2
[2] See Fig. 1 in main text for catalyst dyad D. A and B form similar complex D .
model model model
S10