128.1, 128.2, 128.8, 128.9, 130.1 and 130.2 (Ar-CH), 138.8 and
(±)-2,4-Di-O-benzyl-1-O-diphenoxyphosphoryl-6-O-propyl-
cyclohexane-1,2,4,6-tetraol 35
138.9 (Ar-C quaternary), 150.4 (Ar-C quaternary, 2JCP 8.1) and
2
150.5 (Ar-C quaternary, JCP 8.6); δP(121.5 MHz; C2HCl3)
Following the procedure used for compound 21, alcohol 34 (1.1
g, 3 mmol) was treated with DMAP (73 mg, 0.6 mmol), dry
Et3N (0.63 cm3, 455 mg, 4.5 mmol) and ClPO(OPh)2 (0.93 cm3,
1.2 g, 4.5 mmol) in dry CH2Cl2 (100 cm3) to give phosphate
triester 35 as a colourless oil (1.63 g, 90%) (HRMS: found
[M + H]+, 603.2523. C35H40O7P requires 603.2512); δH (200
MHz; C2HCl3) 0.85 (3 H, t, OCH2CH2CH3), 1.35–1.6 (4 H,
m, OCH2CH2CH3 and 2 × secondary-H), 2.2–2.3 (1 H, m,
secondary-H), 2.4–2.5 (1 H, m, secondary-H), 3.3–3.5 (2 H, m,
OCH2CH2CH3), 3.7–3.85 (2 H, m, 2 × tertiary-H), 4.05–4.1 (1
H, m, tertiary-H), 4.35–4.55 (4 H, m, 2 × OCH2Ph), 4.5–4.6 (1
H, m, 1-H) and 7.1–7.4 (20 H, m, Ar-H); δC(75.5 MHz; C2HCl3)
11.1 (OCH2CH2CH3), 23.7 (OCH2CH2CH3), 34.4 and 36.0 (3-C
and 5-C), 71.1 (OCH2Ph), 71.5 (4-C), 72.3 (OCH2CH2CH3),
72.7 (OCH2Ph), 75.0 (C tertiary, 3JCP 5.9), 75.9 (C tertiary), 83.4
Ϫ12.0; m/z (EI) 575 (20%, [M + H]+), 341 {15, [M Ϫ
(PhO)2PO]+}, 251 {58, [(PhO)2PO2H2]+}, 233 {13, [(PhO)2PO]+}
and 91 (100, [C7H7]+).
(±)-2,4-Di-O-benzyl-1-O-dibenzyloxyphosphoryl-6-O-methyl-
cyclohexane-1,2,4,6-tetraol 33
Following the procedure used for compound 22, phosphate
triester 32 (1.2 g, 2.1 mmol) was reacted with benzyl alcohol
(0.41 cm3, 433 mg, 4 mmol) and NaH (60% dispersion in oil;
160 mg, 4 mmol) in THF (100 cm3) to give phosphate triester 33
as a colourless oil (785 mg, 62%) (HRMS: found [M + H]+,
603.2520. C35H40O7P requires 603.2512); νmax(neat)/cmϪ1 1273s,
1106s, 1023s, 931s, 740s and 696s; δH (500 MHz; C2HCl3) 1.3–1.4
(2 H, m, 2 × secondary-H), 2.18–2.23 (1 H, m, secondary-H),
2.43–2.46 (1 H, m, secondary-H), 3.35 (3 H, s, OCH3), 3.6–3.65
(1 H, m, tertiary-H), 3.65–3.75 (1 H, m, 4-H), 3.98–4.03 (1 H,
m, tertiary-H), 4.28–4.32 (1 H, m, 1-H), 4.4–4.5 (4 H, s,
2 × OCH2Ph), 4.95–5.1 (4 H, m, 2 × POCH2Ph) and 7.25–7.5
(20 H, Ar-H); δC(50.3 MHz; C2HCl3) 34.5 and 35.2 (C second-
2
(1-C, JCP 6.2), 120.5, 120.6, 120.7, 125.7, 125.7, 127.9, 128.0,
128.1, 128.2, 128.8, 128.9 and 130.1 (Ar-CH), 138.8 and 138.9
(Ar-C quaternary), 150.5 (Ar-C quaternary, 2JCP 8.2) and 150.6
2
(Ar-C quaternary, JCP 8.8); δP(121.5 MHz; C2HCl3) Ϫ12.2;
m/z (EI) 603 (30%, [M + H]+), 261 {22, [(M + H) Ϫ (PhO)2-
PO2H2 Ϫ C7H7]+}, 251 {66, [(PhO)2PO2H2]+} and 91 (100,
[C7H7]+).
2
ary), 57.8 (OCH3), 69.5 (POCH2Ph, JCP 5.1), 69.7 (POCH2Ph,
2JCP 5.5), 71.2 (OCH2Ph), 71.6 (4-C), 72.8 (OCH2Ph), 75.7
3
2
(C tertiary), 76.6 (C tertiary, JCP 6.0), 81.8 (1-C, JCP 6.3),
128.0, 128.1, 128.3, 128.8, 128.9, 129.0 and 129.0 (Ar-CH) and
138.9 (Ar-C quaternary); δP(121.5 MHz; C2HCl3) Ϫ1.25; m/z
(EI) 603 (15%, [M + H]+) and 91 (100, [C7H7]+).
(±)-2,4-Di-O-benzyl-1-O-dibenzyloxyphosphonyl-6-O-propyl-
cyclohexane-1,2,4,6-tetraol 36
Following the procedure used for compound 22, phosphate tri-
ester 35 (1.5 g, 2.5 mmol) was reacted with benzyl alcohol (0.49
cm3, 510 mg, 4.75 mmol) and NaH (60% dispersion in oil; 190
mg, 4.75 mmol) in dry THF (100 cm3) to give the phosphate
triester 36 as a colourless oil (945 mg, 60%) (Found: C, 69.85;
H, 6.8. C37H43O7P requires C, 70.45; H, 6.85%) (HRMS: found
M+, 631.2810. C37H44O7P requires 631.2825); δH (500 MHz;
C2HCl3) 0.8 (3 H, t, OCH2CH2CH3), 1.38–1.42 (2 H, m, 2 ×
secondary-H), 1.47–1.53 (2 H, m, OCH2CH2CH3), 2.13–2.17
(1 H, m, secondary-H), 2.38–2.42 (1 H, m, secondary-H), 3.4–
3.5 (2 H, m, OCH2CH2CH3), 3.7–3.8 (2 H, m, 2 × tertiary-
H), 4.08–4.12 (1 H, m, tertiary-H), 4.34–4.38 (1 H, m, 1-H),
4.4–4.6 (4 H, m, 2 × OCH2Ph), 5.0–5.15 (4 H, m,
2 × POCH2Ph) and 7.2–7.4 (20 H, m, Ar-H); δC(50.3 MHz;
C2HCl3) 11.0 (OCH2CH2CH3), 23.8 (OCH2CH2CH3), 34.5 and
35.9 (3-C and 5-C), 69.6 (POCH2Ph, 2JCP 5.5), 69.7 (POCH2Ph,
2JCP 5.8), 71.1 (OCH2Ph), 71.6 (4-C), 72.2 (OCH2CH2CH3), 72.8
(±)-6-O-Methyl-1-O-phosphonatocyclohexane-1,2,4,6-tetraol
bis(cyclohexylammonium) salt 5
Following the procedure used for compound 2, phosphate tri-
ester 33 (500 mg, 0.83 mmol) was treated with sodium metal
(152 mg, 6.6 mmol) in liquid ammonia (20 cm3) at Ϫ78 ЊC to
give phosphate 5 as a white solid (271 mg, 74%), mp >200 ЊC
(decomp.) (HRMS: found [M Ϫ C6H14N Ϫ PO4]+, 145.0869.
2
C7H13O3 requires 145.0865); δH (500 MHz; H2O) 1.1–1.2 (2 H,
m, 2 × 4-H of Cha), 1.25–1.35 (8 H, m, 4 × 2-H and 4 × 3-H of
Cha), 1.35–1.45 (1 H, m, 5-H), 1.55–1.6 (1 H, m, 3-H), 1.6–1.65
(2 H, m, 2 × 4-H of Cha), 1.72–1.82 (4 H, m, 4 × 3-H of Cha),
1.9–2.0 (4 H, m, 4 × 2-H of Cha), 2.05–2.1 (1 H, m, 3-H), 2.35–
2.4 (1 H, m, 5-H), 3.1–3.15 (2 H, m, 2 × 1-H of Cha), 3.43 (3 H,
s, OCH3), 3.58–3.62 (1 H, m, 6-H), 3.94–3.98 (1 H, m, 4-H),
3.96–4.02 (1 H, m, 1-H) and 4.3–4.33 (1 H, m, 2-H); δC(125.6
MHz; 2H2O) 24.1 (3-C of Cha), 24.6 (4-C of Cha), 30.7 (2-C of
Cha), 36.1 (5-C), 37.4 (3-C), 50.7 (1-C of Cha), 57.0 (OCH3),
3
(OCH2Ph), 75.1 (C tertiary, JCP 6.6), 75.7 (C tertiary), 82.0
2
(1-C, JCP 6.4), 127.6, 127.9, 128.0, 128.1, 128.3, 128.4, 128.5
2
3
64.8 (4-C), 67.6 (2-C), 76.8 (1-C, JCP 5.5) and 77.5 (6-C, JCP
6.7); δP(121.2 MHz; 2H2O) 3.0; m/z (FAB-MS) 319 (1%,
[M + 2K + H]+), 281 (8, [M + K + 2H]+), 243 (7, [M + 3H]+)
and 147 (100), where M is the molecular weight of the phos-
phate dianion; m/z (CI) 145 (26, [C7H13O3]+) and 127 (100).
and 128.6 (Ar-CH) and 136.3, 136.4, 136.5 and 139.0 (Ar-C
quaternary); δP(121.5 MHz; C2HCl3) Ϫ1.25; m/z (EI) 631 (1%,
[M + H]+), 539 (4, [M Ϫ C7H7]+), 279 {11, [(BnO)2PO2H2]+} and
91 (100, [C7H7]+).
(±)-1-O-Phosphonato-6-O-propylcyclohexane-1,2,4,6-tetraol
bis(cyclohexylammonium) salt 6
(±)-2,4-Di-O-benzyl-6-O-propylcyclohexane-1,2,4,6-tetraol 34
Following the procedure used for compound 19, propan-1-ol
(0.72 cm3, 577 mg, 9.6 mmol) was reacted with epoxide 17
(1.5 g, 4.8 mmol) to give alcohol 34 as a colourless oil (1.26 g,
71%) (HRMS: found [M + H]+, 371.2240. C23H31O4 requires
371.2222); δH (200 MHz; C2HCl3) 0.9 (3 H, t, OCH2CH2CH3),
1.2–1.4 (2 H, m, 2 × secondary-H), 1.5–1.7 (2 H, m, OCH2-
CH2CH3), 2.3–2.4 (1 H, m, secondary-H), 2.4–2.55 (1 H, m,
secondary-H), 3.35–3.6 (4 H, m, OCH2CH2CH3 and 2 × H ter-
tiary), 3.6–3.8 (1 H, m, tertiary-H), 3.95–4.0 (1 H, m, tertiary-
H), 4.5 (2 H, s, OCH2Ph), 4.6 (2 H, s, OCH2Ph), 7.2–7.5 (10 H,
Ar-H); δC(75.5 MHz; C2HCl3) 11.1 (OCH2CH2CH3), 23.8
(OCH2CH2CH3), 34.6 and 35.9 (3-C and 5-C), 71.1 (OCH2Ph),
71.7 (OCH2CH2CH3), 72.2 (4-C), 72.5 (OCH2Ph), 76.1 and 76.7
(2-C and 6-C), 77.2 (1-C), 128.0, 128.1, 128.2, 128.7, 128.8 and
130.0 (Ar-CH) and 138.8 and 138.9 (Ar-C quaternary); m/z
(EI) 371 (10%, [M + H]+), 279 (23, [M Ϫ C7H7]+), 264 (10,
[M Ϫ C7H7O]+) and 91 (100, [C7H7]+).
Following the procedure used for compound 2, phosphate tri-
ester 36 (630 mg, 1 mmol) was reacted with sodium metal (184
mg, 8 mmol) in liquid ammonia (20 cm3) at Ϫ78 ЊC to give
phosphate 6 as a white solid (337 mg, 72%), mp >200 ЊC
(decomp.) (HRMS: found [M + 2K + H]+, 347.0077.
C9H18K2O7P requires 347.0064, where M+ is the molecular
weight of the free acid); δH (500 MHz; 2H2O) 0.8 (3 H, t,
OCH2CH2CH3), 1.1–1.2 (2 H, m, 2 × 4-H of Cha), 1.25–1.35 (8
H, m, 4 × 2-H and 4 × 3-H of Cha), 1.35–1.45 (1 H, m, 5-H),
1.55–1.65 (5 H, m, OCH2CH2CH3, 2 × 4-H of Cha and 3-H),
1.75–1.83 (4 H, m, 4 × 3-H of Cha), 1.9–2.0 (4 H, m, 4 × 2-H of
Cha), 2.07–2.13 (1 H, m, 3-H), 2.37–2.42 (1 H, m, 5-H), 3.1–3.2
(2 H, m, 2 × 1-H of Cha), 3.58–3.68 (2 H, m, OCH2CH2CH3),
3.7–3.75 (1 H, m, 6-H), 3.96–4.0 (1 H, m, 1-H), 4.0–4.04 (1 H,
m, 4-H) and 4.3–4.38 (1 H, m, 2-H); δC(125.6 MHz; 2H2O) 10.1
(OCH2CH2CH3), 22.8 (OCH2CH2CH3), 24.1 (3-C of Cha), 24.6
(4-C of Cha), 30.7 (2-C of Cha), 37.1 (5-C), 37.6 (3-C), 50.7 (1-
J. Chem. Soc., Perkin Trans. 1, 1997
667