Modular Furanoside Phosphite-Phosphoroamidites
FULL PAPERS
2
2
1
1
.05 (m, 3H, CH allyl), 1.19 (s, 3H, CH ), 1.25 (m, 6H,
JP, P =80.5 Hz), 147.3 (d, 1P, PÀN, J =80.5 Hz); H NMR
3
3
P, P
CH allyl and CH ), 3.21 (m, 1H, H-5), 3.43 (m, 2H, H-2
(CD Cl , 233 K): d=0.98 (m, 2H, CH ), 1.15 (m, 2H, CH ),
2 2 2 2
3
3
and NH), 3.57 (m, 1H, H-5’), 3.86 (m, 1H, CH allyl termi-
1.21 (s, 3H, CH ), 1. 1.32 (s, 9H, CH t-Bu), 1.35 (s, 12H,
3
3
,
nal), 4.20 (m, 1H, H-4), 4.29 (m, 1H, CH allyl terminal),
CH and CH , t-Bu), 1.47 (s, 18H, CH , t-Bu), 1.50 (s, 18H,
3 3 3
4
1
.83 (m, 1H, H-3), 5.33 (m, 1H, CH allyl central), 5.39 (d,
CH , t-Bu), 1.53 (s, 9H, CH , t-Bu), 1.62 (s, 9H, CH , t-Bu),
3
3
3
3
13
H, H-1, J1 =3.6 Hz), 7.2–7.8 (m, 20H, CH=); C NMR
1.79 (m, 2H, CH ), 3.52 (m, 1H, H-5), 3.73 (m, 1H, H-5’),
,2
2
(
CD Cl , 253 K): d=0.2–2.0 [Si
A
H
U
G
R
N
U
G
4.11 (m, 2H, NH, H-4), 4.41 (m, 1H, CH allyl terminal),
2
2
3
3
3
JC,P =7.5 Hz), 18.3 (d, CH allyl, JC,P =7.2 Hz), 26.2 (CH ),
4.62 (m, 1H, H-3), 4.71 (m, 1H, H-2), 5.12 (m, 1H, CH allyl
3
3
3
2
8
7.3 (CH ), 37.2 (m, C-5), 78.9 (C-4), 80.1 (C-3), 83.5 (C-2),
central), 5.81 (d, 1H, H-1, J =4.0 Hz), 5.98 (m, 1H, CH
3
1,2
1
3
6.1 (d, CH allyl trans to PÀO, J =35.2 Hz), 96.9 (d, CH
allyl terminal), 7.1–7.8 (m, 8H, CH=); C NMR (CD Cl ,
C,P
2 2
allyl trans to PÀN, J =34.7 Hz), 105.3 (C-1), 113.9 (CMe ),
233 K): d=18.3 (CH ), 26.3 (CH ), 26.8 (CH ), 28.2 (b,
2 3 3
C,P
2
1
17.9 (m, CH allyl central), 120.0–156.0 (aromatic carbons).
CH ), 31.1–32.7 (CH , t-Bu), 35.2–36.1 (C, t-Bu), 38.7 (m, C-
2
3
3
1
Isomer B (55%); P NMR (CD Cl , 253 K): d=141.5 (d,
1
5), 74.9 (b, C-3 and CH allyl trans to PÀO), 77.0 (C-4), 78.0
2
2
2
2
P, PÀO, JP, P =147.2 Hz), 142.6 (d, 1P, PÀN, JP, P
=
(C-2), 101.9 (d, CH allyl trans to PÀN, J =37.0 Hz), 104.2
C,P
1
147.2 Hz); H NMR (CD Cl , 253 K): d=0.30–0.90 [m, 36H,
(C-1), 114.5 (m, CH allyl central), 115.3 (CMe ), 124.0–150.0
2
2
2
3
1
Si
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
(CH ) ], 1.11 (m, 3H, CH allyl), 1.22 (s, 3H, CH ), 1.29
(aromatic carbons). Minor isomer B (45%); P NMR
3
3
3
3
2
(
m, 3H, CH ), 1.33 (s, 3H, CH allyl), 3.33 (m, 2H, H-5 and
(CD Cl , 233 K): d=144.4 (d, 1P, PÀO, J =79.3), 149.4 (d,
3
3
2
2
P, P
2
1
NH), 3.49 (m, 1H, H-2), 3.57 (m, 1H, H-5’), 3.93 (m, 1H,
CH allyl terminal), 4.20 (m, 1H, H-4), 4.33 (m, 1H, CH allyl
1P, PÀN, J =79.3); H NMR (CD Cl , 233 K): d=0.98 (m,
P, P
2
2
2H, CH ), 1.15 (m, 2H, CH ), 1.29 (s, 3H, CH ), 1. 1.33 (s,
2 2 3
terminal), 4.89 (m, 1H, H-3), 5.29 (m, 1H, CH allyl central),
9H, CH , t-Bu), 1.35 (s, 21H, CH and CH , t-Bu), 1.47 (s,
8H, CH , t-Bu), 1.57 (s, 27H, CH , t-Bu), 1.62 (s, 9H, CH ,
3 3 3
3
3
3
3
5
.43 (d, 1H, H-1, J1,2 =3.6 Hz), 7.2–7.8 (m, 20H, CH=);
1
3
C NMR (CD Cl , 253 K): d=0.2–2.0 [Si
A
H
U
G
R
N
U
G
t-Bu), 1.79 (m, 2H, CH ), 3.55 (m, 1H, H-5), 3.62 (m, 1H,
2
2
3
3
2
CH3 allyl, JC,P =7.2 Hz), 18.8 (d, CH3 allyl, JC,P =7.6 Hz),
H-5’), 4.11 (m, 2H, NH, H-4), 4.49 (m, 1H, CH allyl termi-
nal), 4.62 (m, 1H, H-3), 4.77 (m, 2H, H-2 and CH allyl ter-
minal), 4.98 (m, 1H, CH allyl central), 5.85 (d, 1H, H-1,
2
8
1
1
6.5 (CH ), 27.8 (CH ), 37.8 (m, C-5), 78.9 (C-4), 80.5 (C-3),
3 3
3.8 (C-2), 86.4 (d, CH allyl trans to PÀO, J =35.2 Hz),
C,P
3
13
01.3 (d, CH allyl trans to PÀN, J =35.0 Hz), 105.3 (C-1),
J1,2 =4.0 Hz), 7.1–7.8 (m, 8H, CH=); C NMR (CD Cl ,
C,P
2 2
14.1 (CMe ), 117.5 (m, CH allyl central), 120.0–156.0 (aro-
233 K): d=18.7 (CH ), 26.4 (CH ), 27.0 (CH ), 28.2 (b,
2 3 3
2
matic carbons); anal. calcd. (%) for C H BF NO P PdSi :
CH ), 31.1–32.7 (CH , t-Bu), 35.2–36.1 (C, t-Bu), 38.7 (m, C-
6
5
77
4
8
2
4
2
3
C 57.08, H 5.67, N 1.02; found: C 57.23, H 5.81, N 0.95.
5), 74.6 (b, C-3), 77.0 (C-4), 78.0 (C-2 and CH allyl trans to
3
[
Pd(h -1,3-cyclohexylallyl)
A
T
N
T
E
N
N
(L1a)]BF
(31): Isomer
A
PÀO), 91.9 (d, CH allyl trans to PÀN, J =36.6 Hz), 104.4
4
C,P
31
(
45%); P NMR (CD Cl , 223 K): d=140.4 (d, 1P, PÀO,
(C-1), 113.8 (m, CH allyl central), 115.3 (CMe ), 124.0–150.0
2
2
2
2
2
1
JP, P =79.3 Hz), 144.8 (d, 1P, PÀN, J =79.3 Hz); H NMR
(aromatic
carbons);
anal.
calcd.
(%)
for
P, P
(
CD Cl , 213 K): d=0.95 (m, 2H, CH ), 1.15 (m, 2H, CH ),
C H BF NO P Pd: C 62.76, H 7.60, N 1.05; found: C
2
2
2
2
70 101
4
8 2
1
3
.25–1.61 (m, 78H, CH and CH , t-Bu), 1.72 (m, 2H, CH ),
.41 (m, 1H, H-5), 3.85(m, 1H, H-5’), 4.31 (m, 2H, H-3, CH
62.89, H 7.63, N 1.01.
3
3
2
3
[Pd(h -1,3-cyclohexylallyl)
A
H
U
T
E
N
N
(L3a)]BF
(33): Isomer
A
4
3
1
allyl terminal), 4.42 (m, 2H, H-2, NH), 4.59 (m, 1H, H-4),
4
3
(57%); P NMR (CD Cl , 223 K): d=140.0 (d, 1P, PÀO,
2
2
3
2
2 1
P, P
.81 (m, 1H, CH allyl central), 5.78 (d, 1H, H-1, J1,2
=
JP, P =76.9 Hz), 145.7 (d, 1P, PÀN, J =76.9 Hz); H NMR
.6 Hz), 5.92 (m, 1H, CH allyl terminal), 7.2–7.8 (m, 8H,
(CD Cl , 213 K): d=0.99 (m, 2H, CH ), 1.17 (m, 2H, CH ),
2
2
2
2
13
CH=); C NMR (CD Cl , 213 K): d=20.3 (b, CH ), 26.5
1.3–1.6 (m, 78H, CH and CH , t-Bu), 1.7.5 (m, 2H, CH ),
2
2
2
3
3
2
(
CH ), 26.8 (CH ), 27.2 (b, CH ), 27.9 (b, CH ), 31.4–33.5
3.25 (m, 1H, NH), 4.05 (m, 1H, H-3), 4.42 (m, 1H, H-4),
4.55 (m, 2H, H-5 and H-5’), 4.58 (m, 1H, H-2), 4.69 (m, 1H,
CH allyl terminal), 5.01 (m, 1H, CH allyl central), 5.80 (d,
3
3
2
2
(CH , t-Bu), 35.2–36.0 (C, t-Bu), 38.0 (m, C-5), 75.0 (m, CH
3
allyl trans to PÀO), 77.8 (C-4), 80.2 (C-2), 83.5 (C-3), 98.7
m, CH allyl trans to PÀN), 105.5 (C-1), 111.4 (m, CH allyl
central), 113.6 (CMe ), 124.0–150.0 (aromatic carbons).
3
(
1H, H-1, J1,2 =3.6 Hz), 5.94 (m, 1H, CH allyl terminal),
1
3
7.2–7.8 (m, 8H, CH=); C NMR (CD Cl , 213 K): d=19.0
2
2
2
3
1
Isomer B (55%); P NMR (CD Cl , 223 K): d=143.1 (d,
1
(b, CH ), 26.3 (CH ), 26.5 (CH ), 28.2 (b, CH ), 31.5–33.5
2
2
2 3 3 2
2
2
1
P, JP, P =72.8 Hz), 147.1 (d, 1P, JP,P =72.8 Hz); H NMR
(CH , t-Bu), 35.2–36.2 (C, t-Bu), 56.3 (m, C-3), 63.8 (m, C-
3
(
CD Cl , 213 K): d=0.95 (m, 2H, CH ), 1.15 (m, 2H, CH ),
5), 77.7 (C-4), 77.7 (b, CH allyl trans to PÀO), 85.6 (C-2),
2
2
2
2
1
3
4
.25–1.61 (m, 78H, CH and CH , t-Bu), 1.72 (m, 2H, CH ),
98.9 (m, CH allyl trans to PÀN), 104.4 (C-1), 113.3 (m, CMe
3
3
2
2
.38 (m, 1H, H-5), 3.80 (m, 1H, H-5’), 4.29 (m, 1H, H-3),
.42 (m, 2H, H-2, NH), 4.53 (m, 2H, H-4 and CH allyl ter-
and CH allyl central), 124.0–150.0 (aromatic carbons).
3
1
Isomer B (43%); P NMR (CD Cl , 223 K): d=144.2 (d,
2 2
2 2 1
minal), 4.81 (m, 1H, CH allyl central), 5.82 (d, 1H, H-1,
1P, JP, P =72 Hz), 149.2 (d, 1P, JP,P =72 Hz); H NMR
(CD Cl , 213 K): d=0.99 (m, 2H, CH ), 1.17 (m, 2H, CH ),
3
J1,2 =3.6 Hz), 5.87 (m, 1H, CH allyl terminal), 7.2–7.8 (m,
2
2
2
2
13
8
2
3
H, CH=); C NMR (CD Cl , 213 K): d=20.3 (b, CH ),
1.3–1.6 (m, 78H, CH and CH , t-Bu), 1.7.5 (m, 2H, CH ),
2
2
2
3
3
2
6.3 (CH ), 26.7 (CH ), 27.2 (b, CH ), 27.9 (b, CH ), 31.4–
3.25 (m, 1H, NH), 4.11 (m, 1H, H-3), 4.38 (m, 1H, H-4),
4.42 (m, 1H, H-5), 4,52 (m ,1H, H-5’), 4.60 (m, 1H, H-2),
4.62 (m, 1H, CH allyl terminal), 4.95 (m, 1H, CH allyl cen-
3
3
2
2
3.5 (CH , t-Bu), 35.2–36.0 (C, t-Bu), 38.0 (m, C-5), 76.3 (m,
3
CH allyl trans to PÀO), 77.9 (C-4), 80.0 (C-2), 83.1 (C-3),
3
9
9.2 (m, CH allyl trans to PÀN), 105.3 (C-1), 111.1 (m, CH
tral), 5.84 (d, 1H, H-1, J =3.6 Hz), 5.86 (m, 1H, CH allyl
1
,2
1
3
allyl central), 113.6 (CMe ), 124.0–150.0 (aromatic carbons);
terminal), 7.2–7.8 (m, 8H, CH=); C NMR (CD Cl , 213 K):
2
2 2
anal. calcd. (%) for C H BF NO P Pd: C 62.76, H 7.60, N
d=19.0 (b, CH ), 26.3 (CH ), 26.7 (CH ), 28.2 (b, CH ),
2 3 3 2
7
0
101
4
8
2
1
.05; found: C 62.55, H 7.71, N 1.09.
31.5–33.5 (CH , t-Bu), 35.2–36.2 (C, t-Bu), 56.5 (m, C-3),
3
3
[
Pd(h -1,3-cyclohexylallyl)
A
T
N
T
E
N
N
(L2a)]BF
(32): Isomer
A
63.3 (m, C-5), 77.5 (C-4), 77.7 (b, CH allyl trans to PÀO),
4
31
(
55%); P NMR (CD Cl , 233 K): d=145.5 (d, 1P, PÀO,
85.5 (C-2), 93.0 (m, CH allyl trans to PÀN), 104.4 (C-1),
2
2
Adv. Synth. Catal. 2009, 351, 1648 – 1670
ꢃ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1667