2
669
Synthesis
T. Shibata et al.
Special Topic
31P NMR: δ = 144.9.
HRMS (ESI): m/z [M + Na] calcd for C30H37NaO PSi: 559.2040; found:
+
5
HRMS (ESI): m/z [M + Na]+ calcd for C31H37NaO P: 543.2271; found:
559.2040.
5
543.2272.
6
-(16-Phenyl-1,11-dioxa[11]paracyclophan-13-yloxy)diben-
zo[d,f][1,3,2]dioxaphosphepine [L2(Ph)]
4
-(1,11-Dioxa[11]paracyclophan-13-yloxy)dinaphtho[2,1-d:1′,2′-
f][1,3,2]dioxaphosphepine [(S )-L4]
Colorless oil; yield: 56.0 mg (69%).
a
Foamy white solid; yield: 100.8 mg (98%); mp 90 °C.
[α]21 +10.3 (c 0.69, CHCl3).
D
[
α]25 +175.9 (c 0.68, CHCl3).
IR (CH Cl ): 2925.5, 2854.1, 1606.4, 1490.7, 1442.4, 1241.9, 1178.3,
1
1H NMR: δ = 7.57–7.50 (m, 4 H), 7.45–7.24 (m, 9 H), 7.18 (s, 1 H), 6.98
D
2
2
139.7, 1033.7, 910.2, 835.0, 769.5, 736.7, 702.0, 599.8, 516.8 cm–1
.
IR (CH Cl ): 2929.3, 2850.3, 1592.9, 1500.4, 1465.6, 1232.3, 1189.9,
1
2
2
–1
151.3, 952.7, 838.9, 740.5, 702.0 cm .
1H NMR: δ = 8.00–7.91 (m, 4 H), 7.55 (dd, J = 9.1, 9.1 Hz, 2 H), 7.47–
(s, 1 H), 4.42–4.26 (m, 2 H), 4.00–3.78 (m, 2 H), 1.90–1.63 (m, 2 H),
1.49–1.33 (m, 2 H), 1.11–0.74 (m, 10 H).
7
(
1
.38 (m, 4 H), 7.30–7.24 (m, 2 H), 7.07 (d, J = 8.6 Hz, 1 H), 6.88–6.81
m, 2 H), 4.33–4.28 (m, 1 H), 4.21–4.15 (m, 3 H), 1.72–1.59 (m, 4 H),
.05–0.78 (m, 10 H).
13C NMR: δ = 152.2, 149.2 (d, J = 4.9 Hz), 149.0 (d, J = 4.9 Hz), 145.5 (d,
J = 3.3 Hz), 143.4 (d, J = 5.8 Hz), 137.9, 131.3 (d, J = 3.0 Hz), 131.1 (d, J =
2.7 Hz), 130.9, 130.3, 130.2, 130.0, 129.3, 129.2, 128.3, 127.1, 126.8,
13C NMR: δ = 156.0, 147.8 (d, J = 4.6 Hz), 147.0 (d, J = 2.4 Hz), 144.8 (d,
J = 2.9 Hz), 144.7, 144.6, 132.8 (d, J = 1.7 Hz), 132.6 (d, J = 1.7 Hz),
125.5, 125.3, 123.7, 122.4, 122.2, 121.7 (d, J = 4.0 Hz), 115.7 (d, J = 6.4
Hz), 71.9, 71.4, 30.1, 29.9, 27.8, 26.1, 26.0, 25.6, 25.3.
31P NMR: δ = 144.9.
131.6, 131.3, 130.4, 129.7, 128.4, 128.3, 127.1, 127.0, 126.3, 126.1,
125.2, 125.0, 123.2, 122.1, 121.8 (d, J = 1.7 Hz), 116.6, 114.1, 114.1,
72.1, 71.5, 30.2, 29.6, 27.7, 26.2, 26.0, 25.9, 25.2.
HRMS (ESI): m/z [M + Na]+ calcd for C33H33NaO P: 563.1958; found:
5
31P NMR: δ = 148.9.
563.1959.
HRMS (ESI): m/z [M + Na]+ calcd for C35H33NaO P: 587.1958; found:
5
587.1957.
6-(16-(4-Methoxyphenyl)-1,11-dioxa[11]paracyclophan-13-
yloxy)dibenzo[d,f][1,3,2]dioxaphosphepine [L2(MeOC H )]
6
4
4
-(1,11-Dioxa[11]paracyclophan-13-yloxy)dinaphtho[2,1-d:1′,2′-
Colorless oil; yield: 33.0 mg (58%).
f][1,3,2]dioxaphosphepine [(R )-L4]
[α]26 +2.21 (c 0.71, CHCl3).
a
D
Compound (R )-L4 was obtained as a mixture with 2b, and could not
be isolated because of its instability.
a
IR (CH Cl ): 2929.3, 2854.1, 1619.9, 1500.4, 1245.8, 1178.3, 1132.0,
2 2
–1
1066.4, 907.0, 838.9, 769.5 cm .
Foamy white solid; yield: 85.1 mg (ca. 80%); mp 70 °C.
IR (CH Cl ): 3396.0, 2935.1, 2858.0, 1567.8, 1486.9, 1280.5, 1189.9,
1H NMR: δ = 7.52–7.23 (m, 10 H), 7.15 (s, 1 H), 7.07–6.94 (m, 3 H),
4.41–4.25 (m, 2 H), 3.86 (s, 3 H), 3.99–3.67 (m, 2 H), 1.87–1.33 (m, 4
H), 1.10–0.74 (m, 10 H).
2
2
–1
1151.3, 902.5, 771.4 cm .
1H NMR: δ = 8.01–7.96 (m, 4 H), 7.60–6.57 (m, 11 H), 4.35–4.12 (m, 4
H), 1.72–1.55 (m, 4 H), 1.09–0.76 (m, 10 H).
13C NMR: δ = 156.0, 147.8 (d, J = 4.6 Hz), 147.0 (d, J = 2.4 Hz), 144.8 (d,
13C NMR: δ = 158.9, 152.2, 149.3 (d, J = 5.0 Hz), 149.2 (d, J = 4.8 Hz),
145.7 (d, J = 2.9 Hz), 143.1 (d, J = 6.0 Hz), 131.5, 131.5, 131.3, 131.3,
130.7 (d, J = 1.2 Hz), 130.5, 130.4, 130.1 (d, J = 1.4 Hz), 129.4, 129.3,
125.6 (d, J = 0.96 Hz), 125.5, 123.5, 122.5 (d, J = 1.4 Hz), 122.4 (d, J =
1.2 Hz), 115.9 (d, J = 6.0 Hz), 113.9, 113.8, 72.0, 71.4, 55.4, 30.3, 30.1,
28.0, 26.2, 26.1, 25.7, 25.4.
J = 2.9 Hz), 144.7, 144.6, 132.8 (d, J = 1.7 Hz), 132.6 (d, J = 1.7 Hz),
131.6, 131.3, 130.4, 129.7, 128.4, 128.3, 127.1, 127.0, 126.3, 126.1,
125.2, 125.0, 123.2, 122.1, 121.8 (d, J = 1.7 Hz), 116.6, 114.1, 114.1,
72.1, 71.5, 30.2, 29.6, 27.7, 26.2, 26.0, 25.9, 25.2.
31P NMR: δ = 147.6.
31P NMR: δ = 147.3.
HRMS (ESI): m/z [M + Na]+ calcd for C34H35NaO P: 593.2063; found:
6
HRMS (ESI): m/z [M + Na]+ calcd for C35H33NaO P: 587.1958; found:
593.2063.
5
587.1959.
6-(16-(4-(Trifluoromethyl)phenyl)-1,11-dioxa[11]paracyclophan-
1
3-yloxy)dibenzo[d,f][1,3,2]dioxaphosphepine [L2(CF C H )]
6-(16-(Trimethylsilyl)-1,11-dioxa[11]paracyclophan-13-
3
6
4
yloxy)dibenzo[d,f][1,3,2]dioxaphosphepine [L2(TMS)]
Colorless oil; yield: 33.4 mg (37%).
Colorless oil; yield: 67.0 mg (83%).
[α]23 +19.0 (c 0.67, CHCl3).
D
[
α]25 +23.3 (c 0.66, CHCl3).
IR (CH Cl ): 2929.3, 2850.3, 1490.7, 1241.9, 1211.1, 1147.4, 1101.2,
2 2
D
–1
885.2, 864.0, 813.8 cm .
IR (CH Cl ): 2925.5, 2865.7, 1606.4, 1500.4, 1429.0, 1429.7, 1193.7,
1
2
2
–1
1H NMR: δ = 7.68–7.65 (m, 4 H), 7.53–7.17 (m, 8 H), 7.17–6.79 (m, 2
157.1, 1087.7, 970.0, 910.2, 860.1, 740.5 cm .
1H NMR: δ = 7.51–7.28 (m, 7 H), 7.22–7.20 (m, 1 H), 7.12 (m, 1 H),
H), 4.42–4.26 (m, 2 H), 4.05–3.70 (m, 2 H), 1.88–1.64 (m, 2 H), 1.50–
1.32 (m, 2 H), 1.20–0.71 (m, 10 H).
6.77 (s, 1 H), 4.35–4.29 (m, 2 H), 4.20–4.11 (m, 2 H), 1.78–1.45 (m, 4
H), 1.11–0.57 (m, 10 H), 0.29 (s, 9 H).
13C NMR: δ = 160.7, 149.1 (dd, J = 4.8, 11.6 Hz), 145.5 (d, J = 6.0 Hz),
13C NMR: δ = 152.5, 149.2, 149.0 (d, J = 5.2 Hz), 145.5 (d, J = 2.4 Hz),
144.3, 144.3, 141.4, 131.3 (d, J = 3.1 Hz), 131.1 (d, J = 2.2 Hz), 130.0,
1
1
29.6, 129.2, 125.5, 125.4, 125.2, 125.2, 123.6, 122.3, 122.2, 115.5,
15.4, 72.0, 71.7, 30.0, 29.8, 27.8, 26.1, 26.0, 25.6, 25.2; the peaks in
1
1
43.2 (d, J = 3.3 Hz), 131.3 (d, J = 3.3 Hz), 131.2 (d, J = 3.0 Hz), 130.0,
30.0, 129.2, 129.1, 129.1, 126.2 (d, J = 1.2 Hz), 125.4, 125.3, 122.4 (d,
the aromatic region are overlapping.
19F NMR: δ = –62.2.
31P NMR: δ = 144.5.
J = 1.5 Hz), 122.2 (d, J = 1.2 Hz), 110.0, 110.0, 72.3, 69.6, 29.6, 29.5,
7.8, 26.5, 26.5, 26.2, 24.7, –0.4.
31P NMR: δ = 146.3.
2
©
Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, 2664–2670