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Pleas eD ad l ot o nn oT tr aa nd sj au cs tt i omn as rgins
Journal Name
ARTICLE
shifts were measured relative to BF
3 2
1
DOI: 10.1039/C8DT04058C
reference. NMR assignments were made based on H–COSY,
A vial was charged with 8-aminoquinoline (144 mg, 1.0 mmol),
1
13
and H– C-HSQC NMR spectroscopy. The elemental analyses
were performed on a Perkin-Elmer 2400 CHN elemental
analyser. Solution magnetic susceptibilities were measured at
the phenyl-substituted phosphonium dimer (309 mg, 0.5
mmol), and sodium(triacetoxy)borohydride (424 mg, 2.0
mmol). 3 Å molecular sieves were added. THF (8 mL) was added
and the blood-red mixture was stirred for 18 h at room
temperature. The solvent was evaporated under vacuum and
the residue was dissolved in DCM (10 mL). An air-free wash of
2
5 °C by a method originally described by Evans. A solution of
the compound in CDCl /cyclohexane (95/5 v/v) was prepared.
The external standard consisted of a flame-sealed capillary
containing CDCl /cyclohexane (95/5 v/v). The chemical shift
3
3
the organic layer with saturated NH
0 mL) was carried out. The organic layer was dried over
Na SO , filtered and dried under vacuum to give an orange-red
oil that was used without further purification (191 mg, 54%).
4
Cl (2x 10 mL) and water (2x
difference of cyclohexane between the inset and the solution
was used to determine the magnetic moment eff. All
measurements were run in duplicate at minimum.
1
2
4
3
1
1
1
P{ H} NMR (202 MHz, CDCl
CDCl ) : 2.55-2.59, m, 2H, (CH
s(br), 1H, (NH), 6.54-6.56, dd (J = 7.7, 1.1 Hz), 1H, (Ar-H), 7.04-
.06, dd (J = 8.2, 1.2 Hz), 1H, (Ar-H), 7.33-7.52, m, 12H, (Ar-H,
3
) : -21.09 ppm. H NMR (500 MHz,
N-(2-(diphenylphosphinyl)ethyl)pyridin-2-amine (1a)
3
2
), 3.48-3.53, m, 2H, (CH ), 6.33,
2
A vial was charged with 2-aminopyridine (94 mg, 1.0 mmol),
phenyl-substituted phosphonium dimer (309 mg, 0.5 mmol),
and sodium(triacetoxy)borohydride (424 mg, 2.0 mmol). THF (6
mL) was added and the mixture was stirred over 3 Å MS for 18
hours. The solvent was removed in vacuo and the residue was
dissolved in DCM (10 mL) and transferred to a 25 mL Schlenk
flask. On the Schlenk line under argon, an air-free wash with
7
PPh
2
), 8.04-8.05, dd (J = 8.2, 1.7 Hz), 1H, (Ar-H), 8.71-8.72, dd (J
13
=
4.2, 1.7 Hz), 1H, (Ar-H). C NMR (126 MHz, CDCl
3
) : 28.39, d,
(
1
1
J = 13.2 Hz) (CH
2
), 40.47, d, ( J = 23.7 Hz) (CH
2
), 104.73, 114.02,
21.45, 127.80 (Ar–C), 128.63, d, (3JCP = 6.8 Hz) (P–PhCH),
2
28.74 (P–Ph; paraCH), 128.84 (Ar–C), 132.87, d, ( JCP = 18.7 Hz)
4
saturated, degassed NH Cl (2x10 mL), and degassed H
2
O (2x10
1
(P–PhCH), 136.03 (Ar–C), 138.18, d, ( JCP = 12.3 Hz) (P–PhC),
mL) was conducted. The solution was dried over MgSO
filtered, and passed through a short neutral alumina plug. The
solvent was removed to give a white solid that was
4
,
1
38.32, 144.33, 146.92 (Ar–C). MS-DART m/z calculated for
+
[
C
23 21 2
H N P] : 357.1515, found: 357.1525.
recrystallized by slow evaporation of a THF/pentane mixture N-(2-(dicyclohexylphosphinyl)ethyl)quinolin-8-amine (2b)
1
(
125 mg, 41%). 31P{ H} NMR (202 MHz, CDCl
3
) : -21.38 ppm.
) : 2.39-2.42, m, 2H, (CH ), 3.42-3.48,
), 4.62, s(br), 1H, (NH), 6.23-6.25, d (J = 8.4 Hz), 1H,
Py-H), 6.53-6.56, m, 1H, (Py-H), 7.32-7.47, m, 11H, (PPh , Py-
The same general procedure was followed as in the synthesis of
a but using the cyclohexyl-substituted phosphonium dimer
321 mg, 0.5 mmol). Orange-red oil that was used without
1
H NMR (500 MHz CDCl
m, 2H, (CH
3
2
2
(
2
(
2
31
1
further purification (209 mg, 57%). P{ H} NMR (202 MHz,
H), 8.06-8.08, m, 1H, (Py-H). MS-DART m/z calculated for
1
CDCl3) : -8.61 ppm. H NMR (500 MHz, CDCl3) : 1.17-1.30,
+
[
C H N
19 20 2
P] : 307.1359, found: 307.1358.
m(br), 10H, (Cy-CH
.79, m(br), 10H, (Cy), 1.85-1.89, m, 2H, (CH
CH ), 6.30, s(br), 1H, (NH), 6.66-6.67, dd (J = 7.7, 1.1 Hz), 1H,
Ar-H), 7.02-7.05, m, 1H, (Ar-H), 7.34-7.40, m, 2H, (Ar-H), 8.03-
2
), 1.57-1.62, m(br), 2H, (Cy-CH) (Cy 1.69-
1
2
), 3.41-3.46, m, 2H,
N-(2-(dicyclohexylphosphinyl)ethyl)pyridin-2-amine (1b)
(
(
2
The same general procedure was followed as in the synthesis of
a but using the cyclohexyl-substituted phosphonium dimer
321 mg, 0.5 mmol). Pale-yellow oil that was used without
further purification (136 mg, 43%). P{ H} NMR (242 MHz,
1
(
8
.05, dd (J = 8.3, 1.7 Hz), 1H, (Ar-H), 8.70-8.71, dd (J = 4.2, 1.7
13
Hz), 1H, (Ar-H). C NMR (126 MHz, CDCl3) : 21.83, d, (J = 17.7
Hz) (P-CH2), 27.36, d, (J = 7.5 Hz) (Cy-CH2), 27.46, d, (J = 11.6
Hz) (Cy-CH2), 29.07, d, (J = 7.7 Hz) (Cy-CH2), 30.41, d, (J = 14.5
Hz) (Cy-CH2), 33.37, d, (J = 11.6 Hz) (Cy-CH), 43.23, d, (J = 30.8
Hz) (P-CH2), Ar–C: 104.84, 113.88, 121.46, 127.92, 128.79,
3
1
1
1
CDCl
3
) : -10.57 ppm. H (500 MHz, CDCl
3
) : 1.16-1.24, m(br),
1
1
1
7
0H, (Cy-CH
2H, (Cy-CH
2
), 1.52-1.57, m(br), 2H, (Cy-CH), 1.66-1.78, m(br),
& P-CH ), 3.35-3.40, q(br), 2H (P-CH ), 4.90, s(br),
2
2
2
H (NH), 6.36, d(br), 1H, (py-H), 6.52-6.55, m, 1H, (py-H), 7.36-
.40, m, 1H, (py-H), 8.07, s(br), 1H, (py-H). MS-DART m/z
1
36.08, 138.31, 144.58, 146.92. MS-DART m/z calculated for
+
[
C
25 33 2
H N P] : 369.2454, found: 369.2459.
+
calculated for [C19
H
31
N
2
P] : 319.2298, found: 319.2304.
N-(2-(diisobutylphosphinyl)ethyl)pyridin-2-amine (1c)
N-(2-(diisobutylphosphinyl)ethyl)quinolin-8-amine (2c)
The same general procedure was followed as in the synthesis of
1
a but using the isobutyl-substituted phosphonium dimer (269 The same general procedure was followed as in the synthesis of
mg, 0.5 mmol). Colourless oil that was used without further 2a but using the isobutyl-substituted -phosphonium dimer (269
3
1
1
purification (106 mg, 40%). P{ H} NMR (242 MHz, CDCl
3
) : - mg, 0.5 mmol). Orange-red oil that was used without further
1
i
31
1
4
CH
CH
4.19 ppm. H (600 MHz, CDCl
), 0.97, d (J = 3.2 Hz), 6H, ( Bu-CH
), 1.65-1.70, m, 4H, ( Bu-CH & CH
.68, s(br), 1H, (NH), 6.34-6.35, dd (J = 8.4, 1.0 Hz), 1H, (py-H), ( Bu-CH
.51-6.53, m, 1H, (py-H), 7.35-7.38, m, 1H, (py-H), 8.05-8.06, m, 3.44-3.48, m, 2H, (CH
H, (py-H). MS-DART m/z calculated for [C15
3
i
) : 0.96, d (J = 3.2 Hz), 6H, ( Bu- purification (187 mg, 59%). P{ H} NMR (202 MHz, CDCl
3
) : -
) : 1.02, d (J = 4.0 Hz), 6H,
), 1.35-1.45, m, 4H,
),
), 6.23, s(br), 1H, (NH), 6.66-6.68, m, 1H,
i
1
3
3
), 1.28-1.36, m, 4H, ( Bu- 42.60 ppm. H NMR (500 MHz, CDCl
3
i
i
i
2
2
), 3.35-3.40, m, 2H, (CH
2
), ( Bu-CH
3
), 1.03, d (J = 4.0 Hz), 6H, ( Bu-CH
3
i
i
4
6
1
2
), 1.70-1.80, m, 2H, ( Bu-CH), 1.85-1.89, m, 2H, (CH
2
2
+
H
27
N
2
P] : 267.1985, (Ar-H), 7.03-7.06, m, 1H, (Ar-H), 7.34-7.41, m, 2H, (Ar-H), 8.03-
8.05, dd (J = 8.2, 1.7 Hz), 1H, (Ar-H), 8.71-8.72, dd (J = 4.2, 1.7
found: 267.1992.
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