Chiral Aryl Diphosphite Ligands Derived from Pyranoside Backbone
FULL PAPERS
Phenyl 3,6-Anhydro-b-d-galactopyranoside (9) and
Phenyl 3,6-Anhydro-b-d-glucopyranoside (12)
2,4-Bis{[(S)-1,1’-binaphthyl-2,2’-diyl] Phosphite}-
phenyl 3,6-Anhydro-b-d-galactopyranoside (2)
Phenyl 6-O-p-tolylsulphonyl-b-d-galactopyranoside (8; 0.65 g,
1.585 mmol) in ethanol (20 mL) was converted by a solution of
sodium hydroxide (20 mL, 1 N) at 80 858C in 2 h into com-
pound 9, which was extracted with ether-acetone (1:1, v/v).
Evaporation of the extract yielded a colourless syrup. Tritura-
tion with ether induced crystallization and a colourless powder
was obtained after recrystallization from ether; yield: 0.372 g
Treatment of in situ formed[17] (S)-(1,1’-binaphthyl-2,2’-dioxy)-
chlorophosphine (2.2 mmol) and compound 9 as described for
compound 1 afforded diphosphite 2, which was purified by
flash chromatography (toluene, Rf ¼0.64) to produce a white
powder; yield: 0.405 g (47%). 31P NMR (202 MHz, CDCl3):
1
d¼137.1 (s, 1P), 140.5 (s, 1P); H NMR (500 MHz, CDCl3):
d¼3.86 (dd, 1H, C2-H, J(1,2) ¼3 Hz, J(2,3) ¼9.5 Hz), 4.11 (d,
1H, C3-H, J(2,3) ¼9.5 Hz), 4.35 (s, 1H, C4-H), 4.38 (d, H, C6-
1
(94%). H NMR (500 MHz, CD3OD): d¼3.80 (dd, 1H, C5-
H, J(5,6) ¼10 Hz, J(4,5) ¼3 Hz), 4.35 (d, 1H, C4-H, J(4,5) ¼3 Hz),
4.15 (m, 4H, C2-H, C3-H, C6-H), 5.24 (s, 1H, C1-H), 6.89
7.22 (m, 5H, Ar-H); anal. calcd. for C12H14O5: C 60.5, H
5.9%; found: C 60.4, H 5.5%.
H, J(6,6) ¼5.0 Hz), 4.46 (dd, 1H, C6-H, J(5,6) ¼10 Hz, J(6,6)
¼
5.0 Hz), 4.88 (dd, C5-H, J(6,5) ¼2 Hz, J(6,5) ¼9.5 Hz), 5.22 (s,
1H, C1-H), 6.73 7.93 (m, 29H, Ar-H); 13C NMR (125 MHz,
CDCl3): d¼71.0 (s, C6), 73.8 (d, C4), 75.8 (s, C3), 77.9 (d,
¼
¼
Treatment of phenyl 6-O-p-tolylsulphonyl-b-d-glucopyra-
noside (11) as described for compound 9 afforded compound
12 as colourless crystals; yield: 0.210 g (53%). 1H NMR
(500 MHz, CD3OD): d¼3.80 (m, 2H, C2-H, C4-H), 4.07 (t,
1H, C5-H), 4.13 (m, 3H, C6-H, C3-H), 5.50 (s, 1H, C1-H),
6.66 7.22 ( m, 5H, Ar-H); anal. calcd. for C12H14O5: C 60.5,
H 5.9; found: C 60.2, H 5.8.
C5), 79.9 (d, C2), 90.4 (s, C1), 118.8 (CH ), 120.5 (CH ),
¼
¼
¼
¼
121.5 (CH ), 121.6 (CH ), 121.9 (CH ), 122.3 (CH ), 122.6
¼
¼
¼
¼
(CH ), 123.7 (CH ), 123.9 (CH ), 124.2 (CH ), 124.9
(CH ), 125.0 (CH ), 125.2 (CH ), 125.3 (CH ), 125.4
(CH ), 126.2 (CH ), 126.3 (CH ), 126.4 (CH ), 126.5
(CH ), 126.8 (CH ), 127.7 (CH ), 128.2 (CH ), 128.3
(CH ), 128.4 (CH ), 128.5 (CH ), 129.1 (CH ), 129.5
(CH ), 130.1 (CH ), 130.5 (CH ), 130.7 (CH ), 130.9
¼
¼
¼
¼
¼
¼
¼
¼
¼
¼
¼
¼
¼
¼
¼
¼
¼
¼
¼
¼
¼
¼
¼
¼
(CH ), 131.2 (CH ), 131.6 (C), 131.7 (CH ), 132.5 (CH ),
¼
¼
132.7 (CH ), 132.8 (CH ), 137.8 (C), 146.8 (C), 147.3 (C),
147.6 (C), 147.7 (C), 147.8 (C), 147.9 (C), 150.4 (C); MS
(5.34ꢀ104 eV): m/e (int (%)¼867 (2.2) [Mþ1], 889 (1.9)
[MþNa], 317 (100), 235 (23), 285 (34).
2,4-Bis{[(R)-1,1’-binaphthyl-2,2’-diyl] Phosphite}-
phenyl 3,6-Anhydro-b-d-galactopyranoside (1)
(R)-(1,1’-Binaphthyl-2,2’-dioxy)-chlorophosphine (2.2 mmol)
was synthesized in situ,[17] dissolved in toluene (5 mL), and pyr-
idine (0.36 mL, 4.6 mmol) was added. Phenyl 3,6-anhydro-b-d-
galactopyranoside (9; 0.238 g, 1 mmol) was azeotropically
dried with toluene (3ꢀ5 mL) and then dissolved in toluene
(10 mL) to which pyridine (0.18 mL, 2.3 mmol) had been add-
ed. The diol solution was transferred slowly at room tempera-
ture to the solution of phosphorochloridite. The reaction mix-
ture was stirred overnight at reflux, and the pyridine salts were
removed by filtration. Evaporation of the solvent gave a white
foam, which was purified by flash chromatography (toluene,
Rf ¼0.68) to produce a white powder; yield: 0.396 g (46%).
31P NMR (202 MHz, CDCl3): d¼133.5 (s, 1P), 146.7 (s, 1P);
2,4-Bis{[(R)-1,1’-binaphthyl-2,2’-diyl] Phosphite}-
phenyl 3,6-Anhydro-b-d-glucopyranoside (3)
Treatment of in situ formed (R)-(1,1’-binaphthyl-2,2’-dioxy)-
chlorophosphine (2.2 mmol) and compound 12 as described
for compound 1 afforded diphosphite 3, which was purified
by flash chromatography (toluene, Rf ¼0.54) to produce a
white powder; yield: 0.324 g (37%). 31P NMR (202 MHz,
CDCl3): d¼109.6 (d, 1P, J(P,P) ¼5.5 Hz), 146.0 (d, 1P, J(P,P)
¼
5.5 Hz ); 1H NMR (500 MHz, CDCl3): d¼3.00 (s, 1H, C3-H),
3.34 (dd, 1H, C2-H, J(2,3) ¼2.5 Hz, J(1,2) ¼10.5 Hz ), 3.65 (t,
1H NMR (500 MHz, CDCl3): d¼3.80 (dd, 1H, C2-H, J(1,2)
¼
3 Hz, J(2,3) ¼20 Hz), 4.09 (d, 1H, C3-H, J(2,3) ¼20 Hz), 4.30 (s,
1H, C4-H), 4.51 (dd, H, C6-H, J(5,6) ¼0.5 Hz, J(6,6) ¼5.0 Hz ),
1H, C5-H), 3.79 (t, 1H, C4-H), 3.90 (d, 1H, C6-H, J(6,6)
¼
10.5 Hz), 3.94 (t, 1H, C6-H), 5.23 (s, 1H, C1-H), 6.44 7.97
(m, 29H, Ar-H); 13C NMR (125 MHz, CDCl3): d¼66.0 (q,
C6), 69.2 (q, C4), 69.5 (s, C3), 71.5 (m, C5), 75.0 (d, C2), 98.7
4.64 (d, 1H, C6-H, J(6,6) ¼5.0 Hz), 4.98 (dd, C5-H, J(6,
¼
5)
2 Hz, J(6,5) ¼8 Hz), 5.24 (s, 1H, C1-H), 6.87 8.04 (m, 29H, Ar-
H); 13C NMR (125 MHz, CDCl3): d¼70.0 (s, C6), 73.5(d,
C4), 74.8 (s, C3), 77.1 (d, C5), 79.0 (d, C2), 97.4 (s, C1), 115.8
¼
¼
¼
(d, C1), 116.3 (CH ), 120.4 (CH ), 120.5 (CH ), 121.3
¼
¼
¼
¼
¼
¼
¼
¼
(CH ), 121.4 (CH ), 121.5 (CH ), 121.9 (CH ), 122.0
(CH ), 120.5 (CH ), 121.4 (CH ), 121.6 (CH ), 122.0
(CH ), 122.1(CH ), 122.6 (CH ), 123.8 (CH ), 123.9
¼
¼
¼
¼
¼
¼
¼
¼
(CH ), 122.1 (CH ), 122.2 (CH ), 122.3 (CH ), 122.8
¼
¼
¼
¼
¼
¼
¼
¼
(CH ), 123.6 (CH ), 124.5 (CH ), 124.6 (CH ), 125.1
(CH ), 124.2 (CH ), 124.3 (CH ), 125.0 (CH ), 125.2
¼
¼
¼
¼
¼
¼
¼
¼
(CH ), 125.2 (CH ), 125.3 (CH ), 125.4 (CH ), 126.3
(CH ), 125.3 (CH ), 125.4 (CH ), 126.2 (CH ), 126.3
¼
¼
¼
¼
¼
¼
¼
¼
(CH ), 126.5 (CH ), 127.3 (CH ), 128.4 (CH ), 128.6
(CH ), 126.4 (CH ), 126.5 (CH ), 126.9 (CH ), 127.0
¼
¼
¼
¼
¼
¼
¼
¼
(CH ), 129.8 (C), 129.9 (CH ), 130.0 (CH ), 130.4 (CH ),
(CH ), 128.2 (CH ), 128.3 (CH ), 128.4 (CH ), 128.5
¼
¼
¼
¼
¼
¼
¼
¼
130.5 (CH ), 130.8 (CH ), 131.1 (CH ), 131.4 (CH ), 131.8
(CH ), 129.0 (CH ), 129.5 (CH ), 130.1 (CH ), 130.5
¼
¼
¼
¼
¼
¼
(CH ), 132.6 (CH ), 133.0 (C), 134.2 (C), 134.5 (C), 138.2
(C), 147.3 (C), 147.8 (C), 147.9 (C), 148.3 (C), 148.4 (C),
148.9 (C), 149.0 (C), 156.8.4 (C); MS (5.07ꢀ104 eV): m/e (int
(%)¼867 (3.2) [Mþ1], 889 (1.1) [MþNa], 317 (100), 235
(19), 285 (50).
(CH ), 130.7 (CH ), 130.9 (CH ), 131.2 (CH ), 131.6 (C),
¼
¼
¼
¼
131.7 (CH ), 132.5 (CH ), 132.7 (CH ), 132.8 (CH ), 137.8
(C), 146.8 (C), 147.1 (C), 147.6 (C), 147.7 (C), 147.8 (C),
147.9 (C), 156.4 (C); MS (5.48ꢀ104 eV): m/e (int (%)¼867
(1.9) [Mþ1], 889 (1.1) [MþNa], 317 (100), 235 (19), 285 (24).
Adv. Synth. Catal. 2004, 346, 947 953
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¹ 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
951