70
3 Theoretical Study of Rh-Catalyzed …
3-334
0.0
(kcal/mol)
3-337
-23.1
3-338ts
-5.8
3-339
-42.0
migratory insertion
-26.8
3-343ts
-42.0
3-341ts
O-H bond cleavage
3-342
-56.8
G(B3-LYP-D3, toluene)
reductive elimination
3-335ts
10.8
3-344
-49.9
C-H bond cleavage
3-345
-80.1
OMe
MeO
Rh
O
O
OAc
Ph
O
Cl
H
3-334
OMe
MeO
Rh
O
O
OAc
Ph
O
Cl
H
3-335ts
K 2 CO 3
OMe
MeO
Rh
OAc
Ph
O
Cl
3-337
K
O
O
OH
O
O
K
OMe
MeO
Rh
O
Cl
3-338ts
O
O
H
OMe
MeO
Rh
O
Cl
K 2 CO 3
3-339
3-336
3-336
3-336
Ph
Ph
OMe
MeO
Rh
O
Cl
3-341ts
Ph
Ph
OMe
MeO
Rh
O
Cl
Ph
Ph
3-342
OMe
MeO
Rh
O
Cl
Ph
Ph
3-343ts
OMe
MeO
Rh Ph
Ph
3-344
O
Cl
OMe
MeO
Rh
OAc
AcO
3-345
Cu(OAC) 2
3-346
O
Cl
R 1
R 2
3-346
oxidation
-22.9
3-347ts
3-340
3-340
3-340
-13.4
3-348ts
3-340
-12.3
3-349ts
3-340
OMe
MeO
Rh
Ph
Cl
O
3-347ts
Ph
OMe
MeO
Rh
O
Cl
3-348ts
Ph
Ph
OMe
MeO
Rh
Cl
O
3-349ts
Ph
Ph
Fig. 3.65 Free energy profiles for Rh(I)-catalyzed C–H activation and asymmetric dearomatization
reaction of 2-naphthols. The values are the relative free energies given in kcal/mol calculated at the
B3-LYP-D3/6-31G(d,p)/def2-TZVPP//ωB97XD/6-31G(d,p)/SDD level of theory in toluene
co-workers [158] reported a Rh(III)-catalyzed phosphoryl-directed C–H bond activation and annulation of arylphosphonic acid monoesters with alkynes for the synthesis
of phosphaisocoumarins with excellent yields and functional group tolerance. The
Cp*Rh(III) complex was used as the active catalyst in this transformation. The KIE
experiment (k H /k D = 5.3) indicated that the ortho C–H bond cleavage is involved in
the rate-determining step (Scheme 3.66).
Zhao group [159] performed a theoretical study to investigate the detailed mechanism of the above reaction in 2014. As shown in Fig. 3.67, the active CpRh(III)
catalyst 3-351 was generated by reaction of CpRh(III)ClO 2 with AgOAc. The
2 mol % [Cp*RhCl 2 ] 2
1.0 eq. Ag 2 CO 3
1.0 eq. AgOAc
t BuOH, 90 C
80 - 90 % yield
+
R
1
P
O
OEt
OH
R
2
R
3
R
1
O
P
O
R
2
R
3
OEt
Scheme 3.66 Rh(III)-catalyzed phosphoryl-directed C–H bond activation and annulation of
arylphosphonic acid monoesters s with alkyne
3 Theoretical Study of Rh-Catalyzed …
3-334
0.0
(kcal/mol)
3-337
-23.1
3-338ts
-5.8
3-339
-42.0
migratory insertion
-26.8
3-343ts
-42.0
3-341ts
O-H bond cleavage
3-342
-56.8
G(B3-LYP-D3, toluene)
reductive elimination
3-335ts
10.8
3-344
-49.9
C-H bond cleavage
3-345
-80.1
OMe
MeO
Rh
O
O
OAc
Ph
O
Cl
H
3-334
OMe
MeO
Rh
O
O
OAc
Ph
O
Cl
H
3-335ts
K 2 CO 3
OMe
MeO
Rh
OAc
Ph
O
Cl
3-337
K
O
O
OH
O
O
K
OMe
MeO
Rh
O
Cl
3-338ts
O
O
H
OMe
MeO
Rh
O
Cl
K 2 CO 3
3-339
3-336
3-336
3-336
Ph
Ph
OMe
MeO
Rh
O
Cl
3-341ts
Ph
Ph
OMe
MeO
Rh
O
Cl
Ph
Ph
3-342
OMe
MeO
Rh
O
Cl
Ph
Ph
3-343ts
OMe
MeO
Rh Ph
Ph
3-344
O
Cl
OMe
MeO
Rh
OAc
AcO
3-345
Cu(OAC) 2
3-346
O
Cl
R 1
R 2
3-346
oxidation
-22.9
3-347ts
3-340
3-340
3-340
-13.4
3-348ts
3-340
-12.3
3-349ts
3-340
OMe
MeO
Rh
Ph
Cl
O
3-347ts
Ph
OMe
MeO
Rh
O
Cl
3-348ts
Ph
Ph
OMe
MeO
Rh
Cl
O
3-349ts
Ph
Ph
Fig. 3.65 Free energy profiles for Rh(I)-catalyzed C–H activation and asymmetric dearomatization
reaction of 2-naphthols. The values are the relative free energies given in kcal/mol calculated at the
B3-LYP-D3/6-31G(d,p)/def2-TZVPP//ωB97XD/6-31G(d,p)/SDD level of theory in toluene
co-workers [158] reported a Rh(III)-catalyzed phosphoryl-directed C–H bond activation and annulation of arylphosphonic acid monoesters with alkynes for the synthesis
of phosphaisocoumarins with excellent yields and functional group tolerance. The
Cp*Rh(III) complex was used as the active catalyst in this transformation. The KIE
experiment (k H /k D = 5.3) indicated that the ortho C–H bond cleavage is involved in
the rate-determining step (Scheme 3.66).
Zhao group [159] performed a theoretical study to investigate the detailed mechanism of the above reaction in 2014. As shown in Fig. 3.67, the active CpRh(III)
catalyst 3-351 was generated by reaction of CpRh(III)ClO 2 with AgOAc. The
2 mol % [Cp*RhCl 2 ] 2
1.0 eq. Ag 2 CO 3
1.0 eq. AgOAc
t BuOH, 90 C
80 - 90 % yield
+
R
1
P
O
OEt
OH
R
2
R
3
R
1
O
P
O
R
2
R
3
OEt
Scheme 3.66 Rh(III)-catalyzed phosphoryl-directed C–H bond activation and annulation of
arylphosphonic acid monoesters s with alkyne