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Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn as rgins
Journal Name
ARTICLE
1
1
1
.88-1.78 (m, 2H, C11-H, C6'-H), 1.68-1.61 (m, 2H, C3'-H, C4'-H), 6a (89%). H NMR (CDCl
3
DOI: 10.1039/C9DT0 03 443B
.32-1.15 (m, 2H, C5'-H, C2'-H), 1.06 (dd, 3H, JHH = 7.0, 3JPH = 13.3, Ph), 7.27-6.85 (m, 13H, C7-Ph, C8-Ph, C9-Ph), 5.31 (dd, 1H, JHH
3
=
C12-H), 1.00-0.93 (m, 1H, C3'-H), 0.95 (d, 3H, JHH = 7.0, C8'-H), 0.85 2.5, 3JPH = 8.7, C3-H), 4.59 (dd, 1H, 3JHH = 9.9, 3JPH = 2.3, C6-H), 3.76
3
d, 3H, 3JHH = 7.0, C9'-H), 0.84 (d, 3H, JHH = 7.0, C10'-H), 0.88-0.76 (ddd, 1H, 3JHH = 2.4, 3JHH = 12.6, 2JPH = 15.0, C2-H), 3.47 (td, 1H, JHH
3
3
=
(
(
m, 2H, C4'-H, C6'-H), 0.43 (ddd, 3H, JHH = 8.3, 3JPH = 14.4, 4JPH = 0.8, 10.9, 3JHH = 4.2, C1'-H), 2.24 (ttd, 1H, 3JHH = 7.0, 3JHH = 7.0, 3JHH = 2.6,
3
C13-H). 13C{ H} NMR (CDCl
(
1
1
, δ, ppm, J, Hz): 176.59 (s, C5), 159.48 C7'-H), 1.81 (br d, 1H, 2JHH = 11.6, C6'-H), 1.68-1.62 (m, 2H, C3'-H,
3
dd, 2JCP = 16.7, 2JCP = 4.6, C8), 139.90 (d, 2JCP = 20.7, ipso-С9Рh), C4'-H), 1.33-1.28 (m, 4H, C11-H, C12-H), 1.27-1.19 (m, 2H, C5'-H,
39.32 (dd, 1JCP = 25.0, 2JCP = 18.5, C9), 138.28 (d, 2JCP = 5.3, ipso- C2'-H), 1.02-0.98 (m, 1H, C3'-H), 0.96 (d, 3H, 3JHH = 7.2, C8'-H), 0.86
С7Рh), 136.17 (dd, 3JCP = 2.2, 3JCP = 1.4, ipso-С8Рh), 130.73 (s, o-C8Ph), (d, 3H, 3JHH = 6.9, C9'-H), 0.88-0.85 (m, 3H, C13-H), 0.85 (d, 3H, JHH
3
=
13
1
1
(
1
30.33 (br, o-C7Ph), 130.00 (dd, 3JCP = 8.4, 4JCP = 2.4, o-C9Ph), 128.14 6.4, C10'-H), 0.85-0.80 (m, 2H, C4'-H, C6'-H). C{ H} NMR (CDCl
3
, δ,
2
2
s, m-C9Ph), 127.44 (s, m-C8Ph), 127.33 (s, m-C7Ph), 127.00 (s, p-C8Ph), ppm, J, Hz): 176.54 (s, C5), 158.92 (dd, JCP = 18.0, JCP = 4.5, C8),
26.94 (d, 5JCP = 1.9, p-C9Ph), 126.23 (d, 5JCP = 2.4, p-C7Ph), 100.38 (d, 140.42 (dd, 1JCP = 26.0, 2JCP = 19.3, C9), 139.93 (d, 2JCP = 20.2, ipso-
3JCP = 14.5, C3), 77.58 (s, C1'), 76.58 (dd, 1JCP = 28.7, 2JCP = 4.6, C7), С9Рh), 137.68 (d, 2JCP = 5.7, ipso-С7Рh), 136.18 (dd, 3JCP = 2.2, 3JCP
0.69 (d, 1JCP = 31.9, C2), 47.76 (dd, 2JCP = 2.6, 2JCP = 2.6, C6), 47.76 1.4, ipso-С8Рh), 130.67 (s, o-C8Ph), 130.11 (d, 2JCP = 10.8, o-C7Ph),
=
5
(
s, C2'), 39.80 (s, C6'), 34.24 (s, C4'), 31.29 (s, C5'), 26.65 (d, 1JCP
=
129.96 (dd, 3JCP = 8.4, 4JCP = 2.4, o-C9Ph), 128.18 (s, m-C9Ph), 127.46
3
2.9, C11), 25.41 (s, C7'), 23.02 (s, C3'), 22.06 (s, C10'), 20.98 (s, (s, m-C8Ph), 127.38 (s, m-C7Ph), 127.03 (d, 5JCP = 1.9, p-C8Ph), 126.96
C8'), 20.14 (dd, 2JCP = 13.5, JCP = 4.6, C12), 19.63 (dd, 2JCP = 18.9, 3JCP (d, 5JCP = 2.4, p-C9Ph), 126.27 (s, p-C7Ph), 100.32 (d, 3JCP = 14.5, C3),
3
3.8, C13), 15.62 (s, C9'). 31P{ H} NMR (CDCl
1
, δ, ppm, J, Hz): 90.7 77.48 (s, C1'), 76.80 (dd, 1JCP = 26.2, 2JCP = 4.1, C7), 50.87 (d, 1JCP
=
=
(
(
3
d, 1JCP = 203.3, P10), -39.1 (d, 1JCP = 203.3, P1). IR (KBr, cm ): 457 32.4, C2), 47.84 (dd, 2JCP = 3.6, 2JCP = 2.6, C6), 47.73 (s, C2'), 39.84 (s,
-1
w), 496 (w), 578 (w), 645 (w), 696 (s), 739 (m), 756 (m), 772 (m), C6'), 34.24 (s, C4'), 31.29 (s, C5'), 26.93 (d, 1JCP = 36.0, C11), 25.40 (s,
2
8
02 (s), 873 (w), 919 (w), 954 (m), 1026 (br.s, C-O-C), 1103 (br.s, C- C7'), 23.01 (s, C3'), 22.05 (s, C10'), 20.98 (s, C8'), 19.69 (dd, JCP
=
O-C), 1154 (m), 1262 (s), 1347 (w), 1443 (m), 1492 (w), 1597 (w), 16.8, 3JCP = 3.2, C12), 15.62 (s, C9'), 15.45 (dd, 3JCP = 10.5, 4JCP = 1.0,
1
1
1
765 (s, CO), 2863 (m), 2921 (m), 2956 (m), 3024 (w), 3057 (w). C13). 31P{ H} NMR (CDCl
3
, δ, ppm, J, Hz): 73.7 (d, JCP = 198.3, P10), -
-1
[
α]25
D
= -104° (c 0.5, THF). Found: C 74.50, H 7.33, P 10.28. 37.2 (d, 1JCP = 203.3, P1). IR (KBr, cm ): 497 (w), 578 (w), 645 (w),
44
Calculated for C38H O
3 2
P : C 74.74, H 7.26, O 7.86, P 10.14.
695 (s), 739 (m), 756 (m), 772 (m), 802 (s), 873 (w), 955 (m), 1027
(
(
2
7
br.s, C-O-C), 1103 (br.s, C-O-C), 1152 (m), 1262 (s), 1348 (w), 1444
m), 1491 (w), 1498 (m), 1595 (w), 1762 (s, CO), 2862 (m), 2921 (m),
1
, δ, ppm, J, Hz): 5.19 (dd, 1H, JHH = 2.4, 3JPH
3
5
=
3
2
3
b (6%). H NMR (CDCl
3
8.7, C3-H), 4.95 (ddd, 1H, 3JHH = 9.9, 3JPH = 4.3, 3JPH = 2.4, C6-H),
.75-3.65 (m, 1H, C2-H), 3.38 (td, 1H,3JHH = 10.7, 3JHH = 4.2, C1'-H),
.64-2.55 (m, 2H, C11-H), 1.44-1.39 (m, 3H, C12-H), 1.00-0.92 (m,
H, C13-H). 13C{ H} NMR (CDCl
956 (m), 3021 (w). [α]25
D
= -102° (c 0.5, THF). Found: C 74.56, H
.20, P 10.29. Calculated for C38
44
H O
3
2
P : C 74.74, H 7.26, P 10.14.
1
1
, δ, ppm, J, Hz): 4.26 (dd, 1H, JHH = 11.7, 3JPH
3
3
, δ, ppm, J, Hz): 101.7 (C3), 77.9 6b (9%). H NMR (CDCl
C1'), 47.7 (C6), 43.9 (C2), 24.3 (C12), 22.4 (C11), 22.2 (C13) (from = 9.3, C6-H), 3.98 (d, 1H, 2JPH = 9.1, C2-H). 13C{ H} NMR (CDCl
3
1
(
3
, δ,
HSQC spectra). 31P{ H} NMR (CDCl
03.3, P10), -28.6 (d, 1JCP = 203.3, P1).
1
, δ, ppm, J, Hz): 129.5 (d, 1JCP
=
ppm, J, Hz): 52.4 (C2), 48.4 (C6) (from HSQC spectra). 31P{ H} NMR
(CDCl
, δ, ppm, J, Hz): 71.8 (d, 1JCP = 200.7, P10), -21.9 (d, 1JCP
00.7, P1).
1
3
2
3
=
2
1
3
5
=
0
c (4%). H NMR (CDCl
3
, δ, ppm, J, Hz): 4.25 (dd, 1H, JHH = 12.2, 3JPH
9.3, C6-H), 3.96 (d, 1H, 2JPH = 9.2, C2-H), 1.95-1.85 (m, 2H, C11-H), Synthesis
.49 (ddd, 3H, 3JHH = 8.5, 3JPH = 11.2, 4JPH = 0.8, C13-H). 13C{ H} NMR diphosphatricyclo[5.2.1.02,6]-deca-8-ene-3-(L-menthyloxy)-5-one
of
10-isobutyl-7,8,9-triphenyl-4-oxa-1,10-
1
(
(
=
CDCl
3
, δ, ppm, J, Hz): 51.8 (C2), 48.7 (C6), 26.7 (C11), 19.6 (C13) (7a). 0.25 g (1.04 mmol) of (5R)-(L-menthyloxy)-2(5H)-furanone (4)
from HSQC spectra). 31P{ H} NMR (CDCl
1
, δ, ppm, J, Hz): 89.3 (d, 1JCP were added to solution of 0.40 g (1.04 mmol) 3,4,5-triphenyl-1-
isobutyl-1,2-diphosphacyclopenta-2,4-diene (3) in 10 ml toluene
3
203.3, P10), -23.8 (d, 1JCP = 203.3, P1).
and stirred for 20 hours at 60 C. The solution was filtered and the
Synthesis
of
10-propyl-7,8,9-triphenyl-4-oxa-1,10-
solvent was evaporated at reduced pressure to leave 0.62 g (sum
5%) of a mixture of diastereomers (13:1, de = 86%) 7a (major), 7b
diphosphatricyclo[5.2.1.02,6]-deca-8-ene-3-(L-menthyloxy)-5-one
9
(
6a). 0.26 g (1.08 mmol) of (5R)-(L-menthyloxy)-2(5H)-furanone (4)
and 7c (minor). The major diastereoisomer 7a was isolated by slow
precipitation from 3 ml n-hexane at -40 °C. The precipitate was
isolated and dried to give 7a as a pale yellow powder (0.44 g, 68%)
with m.p. 140 C.
were added to solution of 0.4 g (1.08 mmol) 3,4,5-triphenyl-1-
propyl-1,2-diphosphacyclopenta-2,4-diene (2) in 10 ml toluene and
stirred for 22 hours at 60 C. The solution was filtered and the
solvent was evaporated at reduced pressure to leave 0.63 g (sum
9
6
1
4
5%) of a mixture of diastereomers (11:1, de = 83%) 6a (major) and 7a (89%). H NMR (CDCl , δ, ppm, J, Hz): 7.47 (d, 2H, J = 7.8, C7-o-
3 PH
b (minor). The major diastereoisomer 6a was isolated by slow Ph), 7.27-6.85 (m, 13H, C7-Ph, C8-Ph, C9-Ph), 5.29 (dd, 1H, 3JHH
=
precipitation from 3 ml n-hexane at -40 °C. The precipitate was 2.5, 3JPH = 8.6, C3-H), 4.54 (dd, 1H, 3JHH = 9.9, 3JPH = 2.3, C6-H), 3.74
isolated and dried to give 6a as a pale yellow powder (0.46 g, 70%) (ddd, 1H, 3JHH = 2.4, 3JHH = 12.6, 2JPH = 15.0, C2-H), 3.45 (td, 1H,3JHH
=
with m.p. 137 C.
10.9, 3JHH = 4.2, C1'-H), 2.23 (ttd, 1H, 3JHH = 7.0, 3JHH = 7.0, 3JHH = 2.6,
C7'-H), 1.79 (br d, 1H, 2JHH = 11.6, C6'-H), 1.68-1.62 (m, 2H, C3'-H,
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