C. Gennari, U. Piarulli et al.
3
1
scribed to display two singlets ( P NMR) with the same intensity (1:1
5-P(O)
2
O, biphenol/(ꢀ)-borneol: 82% yield; m.p. 888C; [a]
D
=ꢀ5.5 (c=
[
29]
1
3
ratio) at room temperature (without Rh).
1.00 in chloroform); H NMR (400 MHz, CDCl
3
, 258C): d=7.49 (d,
J
(
H,H)=7.6 Hz, 2H, ArH), 7.40–7.36 (m, 2H, ArH), 7.30–7.26 (m, 2H,
General procedure for the synthesis of phosphoramidites (Method B): A
solution of the amine (1 equiv, 3 mmol) and triethylamine (1.13 equiv,
3
ArH), 7.20 (d, J(H,H)=8.0 Hz, 2H, ArH), 4.62–4.56 (m, 1H, CH), 2.26–
2
1
CH ); C NMR (100 MHz, CDCl
3 3
1
1
n˜ max =3069, 3030, 2961, 2881, 2453, 1943, 1601, 1499, 1476, 1438, 1264,
1210, 1188, 1097, 891, 858 cm
.18 (m, 1H, CH), 2.06–2.00 (m, 1H, CH), 1.87–1.62 (m, 2H, CH), 1.32–
.24 (m, 3H, CH), 0.94 (s, 3H, CH ), 0.88 (s, 3H, CH ), 0.77 ppm (s, 3H,
, 258C): d=150.2, 131.6, 131.5, 130.3,
3
.4 mmol, 472.5 mL) in dry toluene (2.6 mL) was added to a solution of
PCl (1 equiv, 3 mmol, 262 mL) in toluene (38 mL), in a Schlenk tube,
3
3
3
1
3
under argon. The reaction mixture was heated to 708C for 6 h, and al-
lowed to cool to room temperature. Triethylamine (2.26 equiv,
29.4, 129.3, 125.3, 122.5, 81.5, 50.2, 48.1, 45.4, 38.4, 28.5, 26.9, 20.4, 19.0,
3
1
3 4
3.8 ppm; P NMR (162 MHz, CDCl , 258C): d=145.4 ppm; IR (CCl ):
6
.78 mmol, 945 mL) was added, and the mixture was cooled to ꢀ788C. A
solution of biphenol (1 equiv, 3 mmol) in toluene/THF 4:1 (7.5 mL) was
added slowly. The reaction mixture was left under stirring overnight, al-
lowing to slowly warm to room temperature. The mixture was filtered
over a pad of Celite, and the solvent removed under reduced pressure.
The crude product was purified either by recrystallisation, or by chroma-
tography, to give the desired compound as a white powder.
ꢀ
1
; HRMS (ESI): m/z: calcd for
+
+
[C22
calcd for C22
H
25NaO
3
P] : 391.1439; found: 391.1427 [M+Na] ; elemental analysis
P: C 71.72, H 6.84; found: C 71.78, H 6.87.
25 3
H O
6-P(O) O, biphenol/(1R,2S)-(ꢀ)-trans-(1-methyl-1-phenylethyl)cyclohex-
2
anol: 79% yield; m.p. 1288C; [a] =ꢀ12.6 (c=1.00 in chloroform);
D
1
Bis-[(S)-1-naphth-1-yl-ethyl]amine and bis-[(R)-1-naphth-1-yl-ethyl]-
3
H NMR (400 MHz, CDCl , 258C): d=7.58–7.10 (m, 13H, ArH), 4.32–
[
34]
amine were synthesized in two steps, as reported in literature. (R,R)-
4.24 (m, 1H, CH), 2.28–2.24 (m, 1H, CH), 1.99–1.92 (m, 1H, CH), 1.76–
1.56 (m, 3H, CH), 1.50 (s, 3H, CH ), 1.46 (s, 3H, CH ), 1.38–1.19 (m,
3
1H, CH); 1.19–0.88 ppm (m, 3H, CH); C NMR (100 MHz, CDCl ,
258C): d=150.3, 149.6, 131.4, 129.9, 129.4, 129.0, 127.9, 126.0, 125.3,
124.9, 124.8, 122.2, 122.0, 121.0, 117.0, 77.5 (d, J(C,P)=16 Hz), 52.6, 40.8,
2
,5-diphenylpyrrolidine and (S,S)-2,5-diphenylpyrrolidine were prepared
3
3
[
35]
[14d]
13
following literature procedure.
3
3,3’,5,5’-Tetramethyl-biphenol
and
[
36]
,3’,5,5’-tetra-tert-butyl-biphenol were prepared following the reported
procedures.
-P(O) O, biphenol/(1S,2R,5S)-(+)-menthol: 97% yield; [a]
c=1.00 in chloroform).
3
1
3
6.8, 30.4, 27.6, 25.6, 24.8, 24.6 ppm; P NMR (162 MHz, CDCl
d=153.4 ppm; IR (CCl ): n˜ max =3065, 3031, 2935, 2859, 1943, 1553, 1499,
476, 1437, 1260, 1210, 1187, 1098, 1016, 900, 847, 830 cm ; HRMS
3
, 258C):
1
(
2
D
=+17.4
4
ꢀ
1
1
2
-P(O)
2
O, biphenol/(1R,2S,5R)-(ꢀ)-menthol: 88% yield; m.p. 988C;
+
(
[
ESI): m/z: calcd for [C27
H
29NaO
M+Na] ; elemental analysis calcd for C27
found: C 72.39, H 6.90.
-P(O) O,
3,3’,5,5’-tetra-tert-butylbiphenol/(1R,2R,3R,5S)-(ꢀ)-isopino-
campheol: 87% yield; m.p. 758C; [a] =+5.3 (c=1.00 in chloroform);
3
P] : 455.1752; found: 455.1743
1
[
a]
D
=ꢀ17.4 (c=1.00 in chloroform); H NMR (400 MHz, CDCl
3
, 258C):
+
29 3
H O
P: C 74.98, H 6.76;
3
3
d=7.49 (d, J(H,H)=7.6 Hz, 2H, ArH), 7.37 (t, J(H,H)=7.6 Hz, 2H,
ArH), 7.30 (t, J(H,H)=7.5 Hz, 2H, ArH), 7.22–7.20 (m, 2H, ArH),
3
7
2
4
1
0
0
2
1
2
.20–4.16 (m, 1H, CH), 2.32–2.27 (m, 1H, CH), 2.25–2.18 (m, 1H, CH),
.73–1.69 (m, 2H, CH), 1.51–1.35 (m, 2H, CH), 1.08–1.04 (m, 3H, CH),
D
1
3
3
H NMR (400 MHz, CDCl , 258C): d=7.53–7.51 (m, 1H, ArH), 7.45–
.99 (d, J(H,H)=6.5 Hz, 3H, CH
3
), 0.96 (d, J(H,H)=7.0 Hz, 3H, CH
3
),
3
3
13
7.43 (m, 1H, ArH), 7.28–7.26 (m, 1H, ArH), 7.19–7.17 (m, 1H, ArH),
4
2
1.50 (s, 18H, tBu), 1.45 (s, 3H, CH ), 1.36 (s, 18H, tBu), 1.20 (d,
(
.88 ppm (d, J(H,H)=6.9 Hz, 3H, CH
3
); C NMR (100 MHz, CDCl
3
,
.75–4.57 (m, 1H, CH), 2.59–2.52 (m, 1H, CH), 2.41–2.36 (m, 1H, CH),
58C): d=156.0, 149.8, 131.8, 130.3, 129.4, 128.1, 125.4, 122.5, 120.3,
18.5, 76.7 (d, J(C,P)=17.4 Hz), 48.9, 44.6, 34.5, 32.2, 25.7, 23.3, 22.5,
.27–2.23 (m, 1H, CH), 2.10–1.94 (m, 2H, CH), 1.87–1.84 (m, 1H, CH),
3
3
1
J
1.4, 16.0 ppm; P NMR (162 MHz, CDCl
CCl ): n˜ max =3068, 3030, 2958, 2871, 1943, 1910, 1600, 1570, 1556, 1545,
499, 1476, 1438, 1386, 1370, 1271, 1249, 1210, 1187, 1097, 1013, 992,
3
, 258C): d=152.8 ppm; IR
3
3
H,H)=7.2 Hz, 3H, CH
s, 3H, CH ); C NMR (100 MHz, CDCl , 258C): d=127.0, 126.9, 125.4,
3 3
3
), 1.06 (d, J(H,H)=10 Hz, 1H, CH), 0.89 ppm
(
4
1
3
(
1
9
3
7
ꢀ
1
+
124.5, 76.7, 48.2, 46.0, 45.7, 42.0, 38.2, 33.9, 31.9, 31.8, 31.6, 27.9, 24.3,
20.5 ppm; P NMR (162 MHz, CDCl , 258C): d=146.7 ppm; IR (CCl ):
3 4
n˜ max =2963, 2907, 2871, 2448, 1945, 1595, 1556, 1545, 1475, 1440, 1397,
1
00 cm ; HRMS (ESI): m/z: calcd for [C22
93.1579 [M+Na] ; elemental analysis calcd for C22
.35; found: C 71.23, H 7.32.
H
27NaO
3
P] : 393.1595; found:
P: C 71.33, H
3
1
+
H
27
O
3
ꢀ1
363, 1260, 1229, 1094, 1018, 937, 879 cm ; HRMS (ESI): m/z: calcd for
3
-P(O)
2
O, biphenol/(1R,2R,3R,5S)-(ꢀ)-isopinocampheol: 76% yield;
+ +
P] : 615.3943; found: 615.3935 [M+Na] ; elemental analysis
1
[C38
H
57NaO
3
m.p. 1068C; [a]
CDCl
7
7
2
1
D
=ꢀ17.0 (c=1.00 in chloroform); H NMR (400 MHz,
3
3
calcd for C38H O P: C 76.99, H 9.69; found: C 77.02, H 9.71.
57 3
3
, 258C): d=7.49 (d, J(H,H)=7.6 Hz, 2H, ArH), 7.38 (t, J(H,H)=
3
3
8-P(O) O,
8
3,3’,5,5’-tetra-tert-butylbiphenol/(1R,2S,5R)-(ꢀ)-menthol:
.6 Hz, 2H, ArH), 7.29 (t, J(H,H)=7.6 Hz, 2H, ArH), 7.21 (t, J(H,H)=
.6 Hz, 2H, ArH), 4.77–4.69 (m, 1H, CH), 2.59–2.52 (m, 1H, CH), 2.41–
.36 (m, 1H, CH), 2.27–2.23 (m, 1H, CH), 2.10–2.03 (m, 1H, CH), 1.99–
.97 (m, 1H, CH), 1.87–1.84 (m, 1H, CH), 1.25 (s, 3H, CH
2
1
4% yield; m.p. 1408C; [a]
D
=ꢀ17.3 (c=1.00 in chloroform); H NMR
3
(400 MHz, CDCl , 258C): d=7.44 (s, 1H, ArH), 7.43 (s, 1H, ArH), 7.19
3
3
), 1.20 (d, J
(s, 1H, ArH), 7.18 (s, 1H, ArH), 4.11–4.06 (m, 1H, CH), 2.25–2.15 (m,
1H, CH), 2.10–1.80 (m, 2H, CH), 1.70–1.55 (m, 2H, CH), 1.50 (s, 18H,
2tBu), 1.50–0.60 (m, 4H, CH), 1.36 (s, 18H, 2tBu), 0.87–0.84 (m, 6H,
2CH
CDCl , 258C): d=150.0, 131.7, 130.3, 129.4, 125.4, 122.5, 79.1, 76.7, 76.6,
58.3, 48.9, 44.5, 34.5, 32.2, 25.7, 23.3, 22.5, 21.4, 16.0 ppm; P NMR
3
(
(
H,H)=7.2 Hz, 3H, CH
s, 3H, CH
3
), 1.15 (d, J(H,H)=10 Hz, 1H, CH), 0.91 ppm
); C NMR (100 MHz, CDCl , 258C): d=150.0, 130.4, 129.4,
25.4, 122.6, 122.4, 76.1 (d, J(C,P)=15 Hz), 48.2, 46.1, 42.0, 38.8, 38.2,
1
3
3
3
3
13
1
3
1
1
1
3 3
), 0.73 ppm (d, J(H,H)=6.9 Hz, 3H, CH ); C NMR (100 MHz,
3
1
4.4, 28.0, 24.3, 20.4 ppm; P NMR (162 MHz, CDCl
47.7 ppm; IR (CCl ): n˜ max =3069, 3029, 2959, 2910, 2872, 1943, 1911,
601, 1567, 1553, 1499, 1476, 1437, 1386, 1370, 1260, 1249, 1210, 1187,
3
,
258C): d=
3
3
1
4
(162 MHz, CDCl
3
, 258C): d=147.0 ppm; IR (CCl
4
): n˜ max =2962, 2870,
ꢀ
1
ꢀ1
097, 996, 942, 897, 857 cm
;
HRMS (ESI): m/z: calcd for
1595, 1558, 1547, 1456, 1413, 1396, 1362, 1093, 1017 cm ; HRMS (ESI):
+
+
+
+
[
C
22
H
27NaO
4
P] : 409.1545; found: 409.1538 [M+Na+H
2
O] ; elemental
m/z: calcd for [C38
mental analysis calcd for C38
.97.
9-P(O)
3
[a] =+9.8 (c=1.00 in chloroform); H NMR (400 MHz, CDCl , 258C):
H
59NaO
3
P] : 617.4099; found: 617.4093 [M+Na] ; ele-
analysis calcd for C22
H
25
O
3
P: C 71.72, H 6.84; found: C 71.80, H 6.86.
59 3
H O
P: C 76.73, H 10.00; found: C 76.69, H
9
4
-P(O)
2
O, biphenol/(1R,2S)-(ꢀ)-trans-2-phenyl-1-cyclohexanol: 63%
1
yield; m.p. 1178C; [a]
D
=ꢀ53.6 (c=1.00 in chloroform); H NMR
2
O, biphenol/(1R)-endo-(+)-fenchol: 78% yield; m.p. 1048C;
1
(
(
2
400 MHz, [D
6
]benzene, 258C): d=7.46–6.90 (m, 12H, ArH), 6.50–6.40
D
3
m, 1H, ArH), 4.50–4.38 (m, 1H, CyH), 2.80–2.65 (m, 1H, CyH), 2.35–
d=7.50 (d, J(H,H)=7.6 Hz, 2H, ArH), 7.44–7.21 (m, 6H, ArH), 3.96 (d,
1
3
3
.20 (m, 1H, CyH), 2.10–1.20 ppm (m, 7H, CyH); C NMR (100 MHz,
]benzene, 258C): d=149.9, 143.9, 130.4, 130.1, 129.5, 129.4, 129.1,
29.0, 128.4, 127.3, 125.5, 125.4, 122.8, 122.7, 79.3 (d, J(C,P)=17 Hz),
J(H,H)=11.6 Hz, 1H, CH), 1.85–1.67 (m, 4H, CH), 1.58–1.40 (m, 3H,
[
D
6
CH), 1.24 (s, 3H, CH
3
), 1.04 (s, 3H, CH
C NMR (100 MHz, CDCl , 258C): d=130.5, 129.6, 125.6, 125.5, 122.9,
89.2 (d, J(C,P)=12.0 Hz), 50.1, 48.8, 41.8, 40.4, 30.6, 26.7, 26.5, 22.2,
3 3
), 0.96 ppm (s, 3H, CH );
1
3
1
5
3
3
1
2.2, 36.0, 34.5, 26.3, 25.7 ppm; P NMR (162 MHz, [D
): n˜ max =3066, 3031, 2961, 2936, 2859, 1942, 1911,
604, 1556, 1498, 1476, 1437, 1260, 1250, 1210, 1187, 1097, 1025, 901, 855,
6
]benzene, 258C):
3
1
d=151.5 ppm; IR (CCl
4
3 4
20.2 ppm; P NMR (162 MHz, CDCl , 258C): d=148.6 ppm; IR (CCl ):
n˜ max =3069, 3030, 2962, 2873, 1944, 1911, 1602, 1569, 1556, 1499, 1476,
1437, 1260, 1210, 1187, 1098, 1015, 904, 857 cm ; HRMS (ESI): m/z:
calcd for [C22
1
8
4
7
ꢀ
1
+
ꢀ1
31 cm ; HRMS (ESI): m/z: calcd for [C24
H
25NaO
O] ; elemental analysis calcd for C24
3.83, H 5.94; found: C 71.15, H 6.16.
4
P] : 431.1388; found:
+
+
+
31.1370 [M+Na+H
2
H
23
O
3
P: C
3
H25NaO P] : 391.1439; found: 391.1423 [M+Na] ; elemen-
tal analysis calcd for C22
H
25
O
3
P: C 71.72, H 6.84; found: C 69.42, H 7.07.
6714
ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2005, 11, 6701 – 6717