Hydrogenation of phosphonate
Russ.Chem.Bull., Int.Ed., Vol. 63, No. 3, March, 2014
695
in D2О and SiMe4, respectively. Hydrogenation was carried out
in a system from the High pressure equipment Co. equipped
with a 10ꢀmL stainless steel autoclave. Optical yields were deterꢀ
mined by HPLC on an Agilent HPꢀ1100 chromatograph using
the Chiralpac AD column (UV detector, 219 nm, hexane—isoꢀ
propanol (99 : 1), 1 mL min–1).7 The retention times for enantiꢀ
omers of diethyl 1ꢀphenylethylphosphonate (2) were 16.2 (S)
and 20.5 (R) min, and that for diethyl 1ꢀphenylvinylphosphoꢀ
nate (1) was 18.2 min. The conversion of compound 1 was deterꢀ
mined using 1H NMR spectroscopy.5 (Sa)ꢀ2ꢀ(Diethylamino)ꢀ
dinaphtho[2,1ꢀd:1´,2´ꢀf][1,3,2]dioxaphosphepine (L1),20 (Sa)ꢀ2ꢀ
(ethyloxy)dinaphtho[2,1ꢀd:1´,2´ꢀf][1,3,2]dioxaphosphepine (L2),21
(Sa)ꢀ2ꢀ(2,2,2ꢀtrifluoroethyloxy)dinaphtho[2,1ꢀd:1´,2´ꢀf][1,3,2]ꢀ
dioxaphosphepine (L3),22 [Rh(COD)2]BF4,23 [Ir(COD)Cl]2,24
and [Ir(COD)2]BARF25 were synthesized according to published
procedures.
Synthesis of diethyl 1ꢀphenylvinylphosphonate (1). Diethyl
1ꢀphenylvinylphosphonate (1) was synthesized according to a proꢀ
cedure scaled and slightly modified in our group.26 Benzaldeꢀ
hyde (10 g, 0.094 mol) and nitromethane (5.73 g, 0.094 mol)
were added to hydroxyethylammonium acetate27 (30 g) washed
with hexane and dried in vacuo (1 Torr). The mixture was stirred
for 15 min, and triethyl phosphite (15.62 g, 0.094 mol) was poured
to the mixture, which was stirred for 1 h at 5 С and kept for 24 h
at room temperature with reflux condenser. The product was
extracted with ethyl acetate (3×25 mL) and purified using flash
chromatography on silica gel, the solvent was evaporated, and
the product was distilled in vacuo to obtain a lightly yellowish oil
(b.p. 160 С, 1.5 Torr). The yield was 7.9 g (35%). The spectral
characteristics of compound 1 correspond to literature data.26
The yield did not exceed 3—5% when using the unmodified
procedure26 with a load of 0.094 mole.
Asymmetric hydrogenation of diethyl 1ꢀphenylvinylphosphonꢀ
ate (1) in CH2Cl2 (general procedure). [Ir(COD)2]BARF or
[Rh(COD)2]BF4 (0.003 mmol) was dissolved in CH2Cl2 (2 mL),
the corresponding ligand L1—L3 (0.006 mmol) was added,
and the solution was stirred for 5 min. In the case of
dimeric [Ir(COD)Cl]2, the weighed sample was 1 mg and conꢀ
tained 0.0015 mmole of the precursor of this metal complex
and 0.006 mmole of the ligand. Diethyl 1ꢀphenylvinylphosꢀ
phonate (1) (72 mg, 0.3 mmol) was added to the obtained
catalysts, the autoclave was filled with hydrogen (50 atm) and
heated to 60 С (10 min), and the mixture was magnetically
stirred. After hydrogen was released, the reaction mixture was
diluted with CH2Cl2 (2 mL) and purified from the catalyst
through a thin layer of silica gel, and the solvents were removed
in vacuo.
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Asymmetric hydrogenation of diethyl 1ꢀphenylvinylphosphonꢀ
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Phosphonate 1 (72 mg, 0.3 mmol) was added to the cataꢀ
lysts prepared (see above) in 0.2 mL of CH2Cl2 from
[Ir(COD)2]BARF (0.003 mmol) and the corresponding ligand
L1—L3 (0.006 mmol) after the solvent was removed in vacuo.
The closed autoclave was first filled with hydrogen to a reꢀ
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Received July 25, 2013;
in revised form February 12, 2014