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OMe
OMe
Pd[(o-tol)3P]2
(S, RFc)-Josiphos
Ar2PH, DMAP
N
N
N
N
Cy2P
PCy2
O
Fe
dioxane
OTf
PAr2
(S, RFc)-Josiphos
[7] See Ref. 4 for a plausible mechanism of this dynamic
kinetic asymmetric transformation.
3a
entry
9
O
T (°C)
ee (%)
Ar2PH
[8] The crystal was obtained from a gram scale reaction.
See supporting information for details.
b
–
1
2
3
4
diphenylphosphine oxide
(p-CF3-C6H4)2PH
60
60
70
80
c
–
38d
50d
(p-CF3-C6H4)2PH
(p-CF3-C6H4)2PH
[9] Attempts to produce PINAP derivatives with
diphenylphosphine oxide and (p-CF3-C6H4)2PH in high
enantioselectivities under our dynamic kinetic
a
Reactions performed with 1.0 equiv of 3a, 4.0 equiv of DMAP, 1.0 mol % of Pd[(o-tol)3P]2,
1.5 mol % of (S, RFc)-Josiphos, 1.05 equiv of Ar2PH (1.0 M in dioxane) at 0.20 M in dioxane in a
glovebox. Ar2PH (1.0 M in dioxane) was added over 8 h. b No reaction. c ~50% conversion.
Determined by chiral SFC analysis; SFC conditions: 35% IPA, 2.5 mL/min, Chiralpak IC
column, tR (min): major = 3.06, minor = 3.98.
d
asymmetric
transformation
conditions
were
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unsuccessful.
[10] To demonstrate the scope of our methodology, the
enantioselective synthesis of Quinazolinap from triflate
10 was attempted, but our reaction conditions led to
poor conversion. Moreover, treatment of triflate 12 with
the optimized conditions for PINAP provided the
QUINAP ligand in diminished selectivity compared to
that with the original reaction conditions4.
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[11] Determined by chiral HPLC analysis: conditions: 10%
IPA 45 min, AD column, tR: (min): minor = 10.5 min,
major = 18.2 min. All the other spectra data were
identical to the reported data. (ref. 1l)
4
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