1380
Russ. Chem. Bull., Int. Ed., Vol. 67, No. 8, August, 2018
Gavrilov et al.
3
.68—3.71 (m, 1 H, CH O); 4.03—4.07 (m, 1 H, CHN); 4.39
С(7)H); 1.77—1.88 (m, 1 H, С(6)H and 1 H, С(7)H); 1.93—2.00
(m, 1 H, C(6)H); 2.66—2.72 (m, 1 H, C(8)H); 3.03—3.10
(m, 2 H, С(4)H); 3.12—3.18 (m, 1 H, С(8)H); 3.29—3.35
(m, 1 H, С(8)H); 3.47—3.55 (m, 1 H, С(8)H, 1 H, С(4)H and
2
3
(
(
s, 2 H, CH N); 4.95 (d, 1 H, CHO, J = 4.1 Hz); 7.19—7.30
2
1
m, 8 H, CHPh); 7.33—7.37 (m, 2 H, CHPh). Н NMR (DMSO-d ),
6
3
4
: 3.34—3.38 (m, 1 H, CH O); 3.40—3.45 (m, 1 H, CH O);
2
2
3
.49—3.53 (m, 1 H, CHN); 4.26 (br. d, 2 H, CH N, J = 6.5 Hz);
1 H, CH O); 3.56—3.61 (m, 1 H, CH O); 3.73 (t, 1 H, С(4)H,
2
2
2
3
3
.86 (d, 1 H, CHO, J = 3.2 Hz); 7.18—7.31 (m, 10 H, CHPh);
J = 7.9 Hz); 3.75—3.79 (m, 1 H, С(5)H)); 3.88—3.95 (m, 1 H,
С(5)H)); 4.11—4.16 (m, 1 H, СHN); 4.39—4.49 (m, 2 H, СH N);
3
3
7.90 (d, 1 H, NH, J = 9.8 Hz); 9.18 (t, 1 H, NH, J = 6.3 Hz).
2
3
3
Synthesis of ligands (S ,R )-5 and (R ,S )-5 (general proce-
5.18 (dd, 1 H, CHO, J = 4.4 Hz, J = 10.1 Hz); 6.81—6.86
C
P
C
P
3
dure). To an intensively stirred solution of phosphorylating reagent
(m, 2 H, CHPh); 6.94 (t, 4 H, CHPh, J = 7.5 Hz); 6.99—7.05
(
S )-4 or (R )-4 (0.48 g, 2 mmol) and Et N (0.56 mL, 4 mmol)
(m, 1 H, CHPh); 7.11—7.15 (m, 1 H, CHPh); 7.17 (t, 2 H, CHPh
,
C
C
3
3
in 20 mL of toluene, compound 3 was added in one portion (0.33 g,
mmol) at 20 C. Reaction mixture was stirred for 24 h at 20 C
and filtered through a short column with SiO /Al O . Filtrate
J = 7.9 Hz); 7.20—7.32 (m, 8 H, CHPh); 7.33—7.37 (m, 2 H,
3
1
CH ); 7.61 (t, 1 H, CH NH, J = 5.7 Hz); 7.91 (d, 1 H, CHNH,
Ph
2
3
J = 9.3 Hz).
2
2
3
was concentrated under reduced pressure (40 Torr); the resulting
Asymmetric sulfonylation of (E)-1,3-diphenylallyl acetate (6)
products (S ,R )-5 and (R ,S )-5 were purified by flash chrom-
with sodium p-toluenesulfinate. Solution of [Pd(allyl)Cl] (0.0037 g,
C
P
C
P
2
atography on silica gel (eluent is toluene).
0.01 mmol) and the corresponding ligand (0.02 mmol or
0.04 mmol) in 5 mL of THF was stirred for 40 min. (E)-1,3-
diphenylallyl acetate (0.1 mL, 0.5 mmol) was added, and the
solution was stirred further for 15 min, then sodium p-toluene-
sulfinate (0.178 g, 1 mmol) was added. The resulting mixture was
stirred for 48 h, added with 5 mL of saturated aqueous NaCl
solution, stirred for 1 h, and extracted with THF (32 mL).
Оrganic phase was washed with saturated aqueous NaCl solution
N´-Benzyl-N´´-{(1S,2S)-1-phenyl-1,3-bis[(2R,5S)-3-phenyl-
,3-diaza-2-phosphabicyclo[3.3.0]octyloxy]propan-2-yl}oxal-
1
amide ((S ,R )-5). Yield 0.64 g (87%), white powder, m.p.
C
P
2
6
1
74—175 C, []
–226.8 (c 0.5, THF). Found (%): C, 65.47;
D
H, 6.36; N, 11.56. C40H46N O P . Calculated (%): C, 65.21;
6
4 2
H, 6.29; N, 11.41. 13С NMR (CDCl ), : 26.3 (s, С(7)); 32.4
3
(
s, C(6)); 32.9 (s, C(6)); 43.7 (s, CH N); 48.4 (d, С(8),
2
2
2
J = 38.4 Hz); 48.7 (d, С(8), J = 37.9 Hz); 54.1 (d, С(4),
(22 mL), dried over MgSO , and filtrated through a thin pad of
4
2
2
J = 7.5 Hz); 54.7 (d, С(4), J = 6.9 Hz); 55.9 (s, CHN); 60.0
d, CH O, J = 6.9 Hz); 63.5 (d, С(5), J = 9.2 Hz); 63.7 (d,
SiO . The solvent was removed under reduced pressure (40 Torr)
2
2
2
(
and recrystallized the resulting solids from 95% ethanol.
2
2
3
С(5), J = 9.2 Hz); 72.5 (s, CHO); 114.9 (d, CH , J = 13.3 Hz);
Precipitated milk-white crystals of product 7 were dried in vacuo
Ph
1
1
18.6 (s, CHPh); 119.0 (s, CHPh); 126.7 (s, CHPh); 127.1 (s, CHPh);
27.6 (s, CHPh); 127.7 (s, CHPh); 127.8 (s, CHPh); 128.5
s, CHPh); 128.8 (s, CHPh); 129.2 (s, CHPh); 137.0 (s, CPh); 138.8
s, CPh); 144.9 (br.s, CPh); 159.5 (s, C=O); 159.6 (s, C=O).
Н NMR (CDCl ), : 1.49—1.58 (m, 2 H, C(6)H); 1.70—1.82
m, 3 H, С(7)H); 1.83—1.89 (m, 1 H, С(7)H); 1.94—2.00 (m, 1 H,
(10 Torr). Results of IR- and H NMR spectroscopy for 7 accord
5
5
1
fully with the earlier published data. Enantiomeric excess of
(
product 7 was determined using HPLC on a chiral stationary
i
(
phase Daicel Chiralcel OD-H (eluent is C H —Pr OH (4 : 1),
6
14
1
–1
0.5 mL min , 254 nm, t(R) = 16.3 min, t(S) = 18.5 min).
3
(
Asymmetric alkylation of (E)-1,3-diphenylallyl acetate (6) with
C(6)H); 2.01—2.07 (m, 1 H, C(6)H); 3.10—3.19 (m, 2 H, С(4)
dimethyl malonate. Solution of [Pd(allyl)Cl] (0.0037 g, 0.01 mmol)
2
H and 1 H, С(8)H); 3.28—3.33 (m, 1 H, С(8)H); 3.34—3.38
and the corresponding ligand (0.02 mmol or 0.04 mmol) in 5 mL
of the corresponding solvent was stirred for 40 min. (E)-1,3-
diphenylallyl acetate (0.1 mL, 0.5 mmol) was added and the
solution was stirred further for 15 min, then dimethyl malonate
(0.1 mL, 0.87 mmol), BSA (0.22 mL, 0.87 mmol), and potas-
sium acetate (0.002 g) were added. The reaction mixture was
stirred for 48 h, diluted with 5 mL of hexane and filtered through
3
(
(
(
m, 1 H, CH O); 3.44 (t, 1 H, С(4)H, J = 8.1 Hz); 3.51—3.59
2
3
m, 2 H, С(8)H); 3.70 (t, 1 H, С(4)H, J = 8.1 Hz); 3.75—3.81
m, 1 H, CH O); 3.96—4.00 (m, 1 H, СHN); 4.02—4.06 (m, 1 H,
2
С(5)H)); 4.18—4.22 (m, 1 H, С(5)H)); 4.42—4.51 (m, 2 H,
3
3
СH N); 5.18 (dd, 1 H, CHO, J = 6.2 Hz, J = 9.9 Hz); 6.66—6.70
2
(
m, 3 H, CHPh); 6.81—6.88 (m, 5 H, CHPh); 6.94 (t, 1 H, CHPh,
J = 7.1 Hz); 6.98—7.02 (m, 4 H, CHPh); 7.23—7.29 (m, 4 H,
3
a thin pad of SiO . Solvents were removed under reduced pres-
2
CHPh); 7.31—7.36 (m, 3 H, CHPh); 7.64 (t, 1 H, CH NH,
sure (40 Torr), the residue was dried in vacuo (10 Torr). Con-
version of substrate 6 and enantiomeric excess of product 8 were
determined using HPLC on a chiral stationary phase Daicel
2
3
3
J = 6.3 Hz); 8.01 (d, 1 H, CHNH, J = 8.8 Hz).
N´-Benzyl-N� -{(1S,2S)-1-phenyl-1,3-bis[(2S,5R)-3-phenyl-
,3-diaza-2-phosphabicyclo[3.3.0]octyloxy]propan-2-yl}oxal-
i
–1
1
Chiralcel OD-H (eluent is C H : Pr OH (99 : 1), 0.3 mL min ,
6 14
amide ((R ,S )-5). Yield 0.61 g (83%), white powder, m.p.
254 nm, t(R) = 28.0 min, t(S) = 29.3 min).
Asymmetric amination of (E)-1,3-diphenylallyl acetate (6) with
C
P
2
6
1
64—165 C, []
+256.8 (c 0.5, THF). Found (%): C, 65.51;
D
H, 6.24; N, 11.30. C40H46N O P . Calculated (%): C, 65.21;
pyrrolidine. Solution of [Pd(allyl)Cl] (0.0037 g, 0.01 mmol) and
6
4
2
2
H, 6.29; N, 11.41. 13С NMR (CDCl ), : 26.3 (s, С(7)); 26.5
the corresponding ligand (0.02 mmol or 0.04 mmol) in 5 mL of
the corresponding solvent was stirred for 40 min. (E)-1,3-
diphenylallyl acetate (0.1 mL, 0.5 mmol) and the solution were
stirred further for 15 min, then freshly-distilled pyridine was
added (0.12 mL, 1.5 mmol). The reaction mixture was stirred for
48 h, diluted with 5 mL of hexane, and filtrated through a thin
3
(
(
s, С(7)); 31.9 (s, C(6)); 32.0 (s, C(6)); 43.7 (s, CH N); 47.2
2
2
2
d, С(8), J = 33.2 Hz); 48.5 (d, С(8), J = 37.6 Hz); 54.1 (d,
2
2
С(4), J = 7.5 Hz); 55.0 (d, С(4), J = 7.5 Hz); 56.4 (s, CHN);
2
2
6
0.7 (d, CH O, J = 5.2 Hz); 62.8 (d, С(5), J = 6.6 Hz); 73.1
2
3
(
s, CHO); 114.9 (d, CHPh
,
J = 11.1 Hz); 115.0 (d, CHPh
,
3
J = 13.3 Hz); 118.9 (s, CHPh); 119.0 (s, CHPh); 126.3 (s, CHPh);
pad of SiO . Solvents were removed under reduced pressure
2
1
27.4 (s, CHPh); 127.8 (s, CHPh); 127.9 (s, CHPh); 128.7
(40 Torr), the residue was dried in vacuo (10 Torr). Conversion
(
(
(
s, CHPh); 129.0 (s, CHPh); 129.1 (s, CHPh); 137.1 (s, CPh); 140.7
of substrate 6 and enantiomeric excess of product 9 were
2
s, CPh); 145.6 (d, C , J = 17.7 Hz); 159.4 (s, C=O); 159.6
determined using HPLC on a chiral stationary phase Daicel
Ph
1
i
s, C=O). Н NMR (CDCl ), : 1.43—1.49 (m, 1 H, C(6)H);
Chiralcel OD-H (eluent is C H :Pr OH:HNEt (200 : 1 : 0.1),
3
6
14
2
–
1
1
.52—1.62 (m, 1 H, С(6)H and 1 H, С(7)H); 1.64—1.75 (m, 2 H,
0.9 mL min , 254 nm, t(R) = 5.0 min, t(S) = 6.1 min ).