spectroscopy of the crude mixture prior to column chromato-
graphy. In procedure 4 volatiles were removed under vacuum
and the conversion determined by 1H or 13C NMR.
(100.62 MHz, CDCl3): δ 29.0 (d, JC,P = 33.2 Hz), 30.9 (d, JC,P
=
28.2 Hz), 119.9 (d, JC,P = 9.1 Hz), 128.1 (s) 128.4 (d, JC,P = 7.0
Hz); 11B NMR (160.41 MHz, CDCl3): δ Ϫ36.05 (dq, JB,H = 96.2
Hz, JB,P = 48.1 Hz); 31P NMR (202.40 MHz, CDCl3): δ 29.56 (br
m); IR (film) 2362 (B–H, s), 2341 (B–H, s), 1622 (C᎐C, w), 1437
᎐
1-Phenyl-2,5-dihydro-1H-phosphole-1-borane 6a
(CH –C᎐C, m) cmϪ1; HRMS (FI): calculated for C7H14BP (M )
ؒ
᎐
2
GP1: diallylphenylphosphino-borane 5a (812 mg, 3.98 mmol),
dichloromethane (196 ml), catalyst 1 (132 mg, 0.16 mmol, 4%),
18 h; flash column chromatography (cyclohexane : toluene, 1 :
1) gave 6a (628 mg, 90%) as a clear oil; GP2: diallylphenyl-
phosphino-borane 5a (52 mg, 0.25 mmol), toluene (12 ml), cata-
lyst 2 (8.5 mg, 0.015 mmol, 6%), 36 h, (48 mg, 100%); GP3: dial-
lylphenylphosphino-borane 5a (53 mg, 0.25 mmol), dichloro-
methane (12 ml), catalyst 3 (8.9 mg, 0.010 mmol, 4%), 18 h, (50
mg, 100%); GP4: diallylphenylphosphino-borane 5a (48 mg,
0.24 mmol), toluene (12 ml), catalyst 4 (20 mg, 0.026 mmol,
11%), 48 h, (40 mg, 100%); 1H NMR (400 MHz, CDCl3): δ 0.92
(3H, br dq, JB,H = 95.2 Hz, JP, H = 10.4 Hz), 2.66–2.96 (4H, m),
6.02 (2H, d, JH,P = 21.3 Hz), 7.43–7.54 and 7.71–7.79 (5H, 2 ×
m); 13C NMR (100.61 MHz, CDCl3): δ 33.2 (d, JC,P 62.4 Hz),
128.6 (d, JC,P = 1.6 Hz), 128.9 (d, JC,P = 9.7 Hz), 131.0 (s) 131.2
(d, JC,P = 3.0 Hz), 131.6 (d, JC,P = 2.5 Hz); 11B NMR (80.25
140.0926. Found: 140.0931.
1-But-3-enyl-2,3,6,7-tetrahydro-1H-phosphepine-1-borane 6e
GP1: tri-but-3-enylphosphino-borane 5e (208 mg, 0.99 mmol),
dichloromethane (50 ml), catalyst 1 (65 mg. 0.079 mmol, 8%),
24 h, (116 mg, 64%); GP2: tri-but-3-enylphosphino-borane 5e
(48 mg, 0.23 mmol), toluene (12 ml), catalyst 2 (16 mg, 0.018
mmol, 8%), 22 h, (73% conv.); GP3: tri-but-3-enylphosphino-
borane 5e (50 mg, 0.24 mmol), dichloromethane (12 ml), cata-
lyst 3 (4 mg, 0.0048 mmol, 2%), 22 h, (100% conv.); GP4: tri-
but-3-enylphosphino-borane 5e (33 mg, 0.16 mmol), toluene
(8.0 ml), catalyst 4 (30.6 mg, 0.040 mmol, 25%) 84 h, >95%
1
conversion; H NMR (500 MHz, CDCl3): δ 0.53 (3H, br dq,
JH,B = 94.2 Hz, JH,P = 10.6 Hz), 1.65–1.78 (4H, m), 1.80–1.87
(2H, m), 2.30–2.43 (4H, m), 2.50–2.59 (2H, m), 5.08 (1H, br dd,
JH,H = 1.0 Hz, 10.0 Hz), 5.15 (1H, ddd, JH,H = 1.0 Hz, 17.5 Hz,
JH,P = 1.5 Hz), 5.78–5.89 (3H, m); 13C NMR (125.73 MHz,
CDCl3): δ 20.8 (d, JC,P = 4.0 Hz), 21.8 (d, JC,P = 33.2 Hz), 23.8
MHz, CDCl3): δ Ϫ36.13 (dq, JB,H = 96.6 Hz, JB,P = 52.6 Hz); 31
NMR (101.25 MHz, CDCl3): δ 25.35 (br m); IR (film) 3019
P
(᎐CH , m), 2318 (B–H, m), 1637 (C᎐C, w), 1621 (C᎐C, w), 1423
᎐
᎐
᎐
2
(CH –C᎐C, w) cmϪ1; HRMS (FI): calculated for C10H14PB (M )
(d, JC,P = 34.2 Hz), 26.6 (s), 115.3 (s), 131.42 (s), 137.5 (d, JC,P
=
=
ؒ
᎐
2
176.0926. Found: 176.0918.
12.1 Hz); 11B NMR (160.41 MHz, CDCl3): δ Ϫ37.58 (dq, JB,H
94.7 Hz, JB,P = 64.1 Hz); 31P NMR (202.40 MHz, CDCl3): δ
20.97 (br m); IR (film) 3022 (᎐CH , w), 2934 (m), 2860 (w), 2364
᎐
1-Phenyl-2,5-dihydro-3-methyl-1H-phosphole-1-borane 6b
2
(B–H, s), 1640 (m, C᎐C), 1445 (w), 1412 (CH –C᎐C, w) cmϪ1
;
᎐
᎐
2
GP1: allyl(2-methylallyl)phenylphosphino-borane 5b (63 mg,
0.29 mmol), dichloromethane (15 ml), catalyst 1 (9.5 mg, 0.012
mmol, 4%), 6 h, (0% conv.); GP2: allyl(2-methylallyl)phenyl-
phosphino-borane 5b (68 mg, 0.31 mmol), toluene (16 ml), cata-
lyst 2 (16 mg, 18.7 µmol, 8%), 30 h, (57% conv.); GP3: allyl(2-
methylallyl)phenylphosphino-borane 5b (135 mg, 0.62 mmol),
dichloromethane (31 ml), catalyst 3 (32 mg, 0.038 mmol, 6%),
26 h, (90% conv.); GP4: allyl(2-methylallyl)phenylphosphino-
borane 5b (47 mg, 0.22 mmol), toluene (11.0 ml), catalyst 4
(16.7 mg, 0.022 mmol, 10%), 60 h, (0% conv.). As the product
was inseparable from the starting material, the spectra were
ؒ
HRMS (FI): calculated for C10H20BP (M ) 182.1396. Found:
182.1405.
1,2-Bis(1-boryl-2,5-dihydro-1H-phosphol-1-yl)ethane 6f
GP1: 1,2-bis(diallylborylphosphino)ethane 5f (193 mg, 0.68
mmol), dichloromethane (52 ml), catalyst 1 (78 mg, 0.095
mmol, 14%), 40 h, (88 mg of 6e, 57% yield); GP2: 1,2-bis(dial-
lylborylphosphino)ethane 5f (171 mg, 0.61 mmol), toluene (60
ml), catalyst 2 (52 mg, 0.061 mmol, 10%), 28 h; flash column
chromatography (toluene : ethyl acetate, 95 : 1) gave 6f (96 mg,
70%) as a clear colourless oil; GP3: 1,2-bis(diallylborylphos-
phino)ethane 5f (104 mg, 0.36 mmol), dichloromethane (18 ml),
catalyst 3 (12 mg, 0.014 mmol, 14%), 21 h, (91 mg of 6f, 100%);
GP4: 1,2-bis(diallylborylphosphino)ethane 5f (50 mg, 0.18
mmol), toluene (9.0 ml), catalyst 4 (16.7 mg, 0.022 mmol, 12%),
60 h, (70% conv.); 1H NMR (500 MHz, CDCl3): δ 0.64 (6H, br
q, JH,B = 94.4 Hz), 1.77 (4H, d, JH,P = 3.5 Hz), 2.55 (4H, br d,
JH,H = 17.0 Hz), 2.69 (4H, br d, JH,H = 17.0 Hz), 5.92 (4H, d, JH,P
1
assigned by comparison with spectra of starting material. H
NMR (500 MHz, CDCl3): δ 0.94 (3H, br q, JH,B = 96.3 Hz,),
2.02 (3H, s), 2.64–2.97 (4H, m), 5.64 (1H, d, JH,P = 23.0 Hz),
7.32–7.55 (2H, m), 7.76–7.80 (3H, m); 13C NMR (100.62 MHz,
CDCl3): δ 19.0 (d, JC,P = 8.0 Hz), 33.4 (d, JC,P = 36.2 Hz), 37.1
(d, JC,P = 38.2 Hz), 122.3 (s), 128.8 (d, JC,P = 10.1 Hz), 131.0 (d,
JC,P = 9.1 Hz), 131.4 (d, JC,P = 2.0 Hz), 131.6 (d, JC,P = 15.1 Hz),
138.4 (d, JC,P = 3.0 Hz); 11B NMR (160.41 MHz, CDCl3): δ
Ϫ35.78 (dq, JB,H = 96.3 Hz, JB,P = 64.2 Hz); 31P NMR (202.40
= 20.5 Hz); 13C NMR (125.72 MHz, CDCl3): δ 18.8 (d, JC,P
27.7 Hz), 28.6 (d, JC,P = 33.9 Hz), 127.9 (s); 11B NMR (160.4
=
MHz, CDCl ): δ 29.52 (br m); IR (film): 3077 (᎐CH , w), 2934,
᎐
3
2
2915, 2854 (CH , w), 2378 (BH , s), 1654 (C᎐C, w), 1437 (CH –
MHz, CDCl3): δ Ϫ36.9 (dq, JB,H = 94.4 Hz, JB,P = 50.3 Hz); 31
P
᎐
3
3
2
C᎐C, s), 1136 (m), 1113 (m), 1062 (s) cmϪ1; HRMS (FI): calcu-
NMR (202.4 MHz, CDCl3): δ 34.61 (br m); IR (film) cmϪ1 2925
(C–H, m), 2854 (C–H, w), 2368 (B–H, s), 2308 (B–H, m), 1618
(C᎐C, w), 1402 (CH –C᎐C, w) cmϪ1; HRMS (FI): calculated for
᎐
ؒ
lated for C11H16BP (M ) 190.1083. Found: 190.1088.
᎐
᎐
2
ؒ
C10H22B2P2 (M ) 225.1305. Found: 225.1300.
1-Allyl-2,3-dihydro-1H-phosphole-1-borane 6d
GP1: triallylphosphino-borane 5d (199 mg, 1.18 mmol), di-
chloromethane (60 ml), catalyst 1 (57 mg, 0.069 mmol, 6%), 23
h; flash column chromatography (cyclohexane : ethyl acetate, 20
: 1) gave 6d (104 mg, 62%) as a clear colourless oil; GP2: tri-
allylphosphino-borane 5d (108 mg, 0.64 mmol), toluene (32
ml), catalyst 2 (43 mg, 0.051 mmol, 8%), 24 h, (93 mg, 100%);
GP3: triallylphosphino-borane 5d (66 mg, 0.39 mmol), di-
chloromethane (20 ml), catalyst 3 (13 mg, 0.016 mmol, 4%), 5 h,
(44 mg, 95%); GP4: triallylphosphino-borane 5d (50 mg, 0.30
mmol), toluene (14 ml), catalyst 4 (20 mg, 0.026 mmol, 9%), 72
h, (95% conv.); 1H NMR (500 MHz, CDCl3): δ 0.69 (3H, br dq,
JH,B 96.3 Hz, JH,P 4.5 Hz), 2.48–2.63 (6H, m), 5.17–5.19 (1H,
m), 5.21–5.24 (1H, m), 5.80 (1H, dddt, JH,H = 7.5 Hz, 10.0 Hz,
17.0 Hz, JH,P = 5.0 Hz), 5.88 (2H, d, JH,P = 20.0 Hz); 13C NMR
1-Phenyl-2,3-dihydro-1H-phosphole 6g
GP2: diallylphenylphosphine 5g (50 µl, 0.25 mmol), toluene
(12 ml), catalyst 2 (17 mg, 0.002 mmol, 8%), 72 h (0%); GP3:
diallylphenylphosphine 5g (50 µl, 0.25 mmol), CH2Cl2 (12 ml),
catalyst 3 (17 mg, 0.021 mmol, 8%), 72 h (0%); GP4: diallyl-
phenylphosphine 5g (30 µl, 0.12 mmol), toluene (7.6 ml),
catalyst 4 (11.5 mg, 0.015 mmol, 12.5%), 84 h (95% conv.). As
product was not separated from starting material, the spectra
1
assigned by comparison with spectra of starting material. H
NMR (400 MHz, CDCl3): δ 2.56–2.88 (4H, m), 5.95 (2H, d,
JH,P = 7.1 Hz), 7.30–7.75 (5H, m); 13C NMR (100.64 MHz,
CDCl3): δ 34.5 (d, JC–P = 10.0 Hz), 128.6 (s), 128.7 (s), 129.7 (d,
JC–P = 5.0 Hz), 131.2 (d, JC–P = 20.0 Hz), 141.6 (d, JC–P
=
O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 3 8 2 0 – 3 8 2 5
3824