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A Predictive Model for the [Rh(esp)]-catalyzed Intermolecular C(sp)-H Bond Insertion of #-carbonyl Ester Carbenes: Interplay Between Theory and Experiment Brett D McLarney, Steven R Hanna, Djamaladdin G Musaev, and Stefan France ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.9b00889 • Publication Date (Web): 04 Apr 2019 Downloaded from http://pubs.acs.org on April 4, 2019
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ACS Catalysis
H
EWG M
Acceptor-only A
EWG
EWG
EDG
EWG
EDG
EDG
M
M
M
Acceptor-Acceptor A-A
Donor-Acceptor D-A
Donor-Donor D-D
H
EDG M
Donor-only D
EWG = ester, ketone, nitro, nitrile, phosphonate, sulfone EDG = aryl, alkeny, alkynyl
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ACS Catalysis 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
(A) Nakamura et al. (2002) R C R H R
H (HCO2)4Rh2
R H
CO2Me
R R R C+ δ
H CO2Me
(HCO2)4Rh2
H H C CO2Me
δ-
(B) this work
CO2Me
R C R H R
L4Rh2 C(O)R
R R R C+ δ L4Rh2
RR CO2Me R C C H C(O)R
Predictive Model H C δ-
OMe O sterics R
O electronics
∆H‡ = f(sterics,electronics)
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ACS Catalysis
A) Overall C-H Insertion Reaction
Carbene Transfer to C–H bond
nitrogen extrusion O
O C*
Me Ca OMe N2 1g
Rh2(esp)2
Ca
O Me
H H
O OMe Rh2(esp)2 2g
Me
O
Me
Me
O OMe Me
H Me
4g
C*
B) Rh-Carbene (2g):
O
Rh
Ca
C*
Top view
Side view
C) C-H Transition State (3g): propane
Me Me
C
δ+
H
OMe
[Rh2] δ- C*
3g
propane
H C* Ca Rh
O
O
Ca
O Ca Me
(LP) C* -> π*(Ca=O) NBO: Orbital Interaction Energy: 42 kcal/mol
C*
Top view
Side view
D) Tabulated Energies, Charges and Bond Distances
ΔH‡/ΔG‡(a) 2g: [Rh2(esp)2]-Carbene 3g: TSC–H -3.4/11.9 (a)
NBO Charges, in |e|
Distances (in Å)
O
C*
C=O
Rh–C*
-0.55 -0.63
-0.01 -0.45
1.228 1.234
1.953 2.301
Calculated Relative to [Rh2(esp)2]-carbene + Substrate, and given in kcal/mol
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ACS Catalysis 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
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ACS Catalysis
O
O
O
OMe Rh2(esp)2
MeO
Me
2a σp = -0.268 ΔH = 3.1 kcal/mol
O
OMe Rh2(esp)2
O OMe Rh2(esp)2
2d σp = 0.062 ΔH = 1.3 kcal/mol
2c σp = 0 ΔH = 1.9 kcal/mol O
Cl
O OMe Rh2(esp)2
H
2b σp = -0.170 ΔH = 2.4 kcal/mol O
F
O
O OMe Rh2(esp)2
2e σp = 0.227 ΔH = 0.5 kcal/mol
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Relative DH≠C-H (kcal/mol)
ACS Catalysis
-0.3
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3.5
X = OMe
3 y = -4.6816x + 1.7605 R² = 0.98342 X = H
2.5 X = Me
2 1.5
X = F
1
X = Cl
0.5 0 -0.2
-0.1
0
0.1
0.2
0.3
Hammett coefficient (spara)
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ACS Catalysis
A. O
PA
R Cα C*H3
R Cα C*H2
5
X 5a (X = OMe) 237.8 5b (X = Me) 236.8 5c (X = H) 234.9 5d (X = F) 234.6 5e (X = Cl) 232.6 5t N 250.2
H
5’ 5f (R = H) 234.0 5g (R = Me) 239.1 5h (R = Et) 238.0 5i (R = neoPent) 237.9 5j (R = i-Pr) 238.1 5k (R = Cy) 238.1 5l (R = t-Bu) 237.9 5m (R = Vinyl) 233.6
R=
5s
O O Cα C* R OMe Rh2(esp)2 2 5n (R = OH) 241.6 5o (R = OMe) 242.9 5p (R = OEt) 242.6 5q (R = OCH2F) 234.4 5r (R = NMe2) 248.5 5v (R = NH2) 248.6
O
5u N 246.8
MeO
5w N Me
242.8
Me
N H
250.3
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X N H 5xa (X = H) 242.1 5xd (X = 4-CF3) 238.3
ACS Catalysis 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47
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ACS Catalysis
O
O
