3.3 Rh-Catalyzed C–H Bond Alkenylation
57
3-227
0.0
G(M06, MeOH)
(kcal/mol)
3-229ts
17.5
3-230
1.7
3-231ts
21.0
3-232
0.0
C-H Bond Cleavage
Migratory Insertion
-3.3
3-236ts
21.3
4-3-83
1.7
3-234ts
25.4
3-228
3-235
4-3-84ts
6.0
-60.4
3-227
-63.4
HOAc
HOAc
3-233
N-H Bond Cleavage
Reductive Elimination
N-O Bond Cleavage
3-227
O N
H
O
3-228
3-229ts
3-230
3-231ts
Ph
Ph
3-234ts
3-235
3-236ts
3-237
3-238ts
3-239
2HOAc
3-240
OH
Ph
Ph
HN Ac
3-240
Protonation
Rh
AcO
OAc
Rh
AcO
O
N
O
O
O
H
Rh
O
N
O
OAc
Rh
O
N
O
3-232
Rh
O
N
O
O
O
H
Rh
O
N
O
Ph
Ph
Rh
O
N
O
Ph
Ph
Rh
O
N
O
Ph
Ph
Rh
O
N
O
Ph
Ph
Rh
O
Ph
Ph
N
O
Rh O
Ph
Ph
N
O
Fig. 3.45 Free energy profiles for Rhodium(III)-catalyzed C–H alkenylation reaction of Nphenoxyacetamides with alkynes. The values are the relative free energies given in kcal/mol
calculated at the M06/6-311++G(d,p)/SDD//B3-LYP/6-31G(d)/LANL2DZ level of theory in MeOH
Fig. 3.46 Free energy profiles for Rhodium(III)-catalyzed C–H alkenylation and cyclization reaction of N-phenoxyacetamides with alkynes. The values are the relative free energies given in
kcal/mol calculated at the B3-LYP/6-31G(d)/LANL2DZ//M06/6-311++G(d,p)/SDD level of theory
in DCM