D. Heller, B. Breit et al.
41.0 ppm; 31P NMR (121 MHz, CD2Cl2): d=37.4 ppm (d, JP-Rh
=
105 (100), 93 (12), 77 (82), 54 (73); HRMS (EI): calcd for C30H34O4Rh2:
664.05617; found: 664.05419 [M]+.
169.8 Hz); MS (ESI-TOF): calcd for [M]+ (C25H24NPRh): 472.0696;
found: 472.0704.
Procedure A: A dry, argon-flushed 1 mL Schlenk vessel with a Teflon
screw cap was charged with [RhACTHNUGRTENNUG(COD)ACHTUNTGREN(NUGN acac)] (2.7 mg, 0.0088 mmol,
[Rh
ACHTUNGTRENNUNG(DPPMP)ACHTUNGTRENNUNG
2.0 mol%), DPPMP (18, 2.4 mg, 0.0088 mmol, 2.0 mol%), and carboxylic
acid (0.44 mmol). The flask was evacuated and filled with argon three
times (note: this was done prior to addition of the carboxylic acid for
liquid/volatile compounds). Freshly distilled THF (0.7 mL) was added
under a flow of argon, and the flask sealed and immersed in a preheated
oil bath (508C). The mixture was stirred for 30 min then allowed to reach
room temperature. (ca. 10 min). Alkyne (0.66 mmol, 1.5 equiv) was
added under a flow of argon, and the flask sealed and immediately im-
mersed in a preheated oil bath (1108C). The mixture was stirred for 4 h
then allowed to reach room temperature (ca. 20 min), filtered through a
pad of silica gel and washed with AcOEt (3ꢄ4 mL) to separate the cata-
lyst. After removal of the solvent under reduced pressure, the crude
product was purified by column chromatography on silica gel.
charged with [Rh
G
ACHTUNGTRENNUNG
was added. After cooling the solution to À788C, a solution of DPPMP
(110 mg, 0.4 mmol) in THF (10 mL) was added dropwise over 15 min.
After stirring at À788C for 30 min, HBF4 in water (40%, 70 mL,
0.44 mmol) was added at À788C. The mixture was stirred for 1 h from
À788C to room temperature. The mixture was concentrated in vacuum,
and the residue washed with diethyl ether. Crystals of [RhACTHNUGTRNEUNG(DPPMP)-
ACHTUNGTRENNUNG(COD)]BF4 suitable for X-ray crystallography were obtained by slow dif-
fusion of diethyl ether into a solution in dichloroethane (210 mg, yield:
1
91%). H NMR (300 MHz, CD2Cl2): d=8.10 (d, J=5.7 Hz, 1H), 7.90 (tt,
J=7.7 Hz, 1.4 Hz, 1H), 7.60–7.67 (m, 5H), 7.41–7.59 (m, 7H), 5.54 (brs,
2H), 4.22 (d, J=11.1 Hz, 2H), 3.90–3.93 (m, 2H), 2.48–2.59 (m, 4H),
2.29–2.35 ppm (m, 4H); 13C NMR (75 MHz, CD2Cl2): d=150.7, 141.1,
133.4, 132.6, 130.0, 128.6, 126.0, 124.8, 107.6, 78.1, 41.2, 32.8, 28.8 ppm;
Procedure B: A dry, argon-flushed 1 mL Schlenk vessel with a Teflon
31P NMR (121 MHz, CD2Cl2): d=42.8 ppm (d,
(ESI-TOF): calcd for [M]+ (C26H28NPRh): 488.1009; found: 488.1020.
[Rh(DPPMP)2H(FBF3)]BF4 (5): A dry, argon-flushed Schlenk tube was
charged with DPPMP (70 mg, 0.25 mmol) and [Rh(COD)(acac)] (39 mg,
J
P-Rh =152.9 Hz); MS
screw cap was charged with [RhACTHNUTRGENN(UG COE)2ACHTUNGTNER(NUGN acac)] (2.7 mg, 0.0088 mmol,
2.0 mol%), DPPMP (18, 2.4 mg, 0.0088 mmol, 2.0 mol%), Cs2CO3
(2.9 mg, 0.0088 mmol, 2.0 mol%), and carboxylic acid (0.44 mmol). The
flask was evacuated and filled with argon three times (note: this was
done prior to addition of the carboxylic acid for liquid/volatile com-
pounds). Freshly distilled THF (0.7 mL) was added and the mixture was
stirred for 10 min at room temperature. Alkyne (0.66 mmol, 1.5 equiv)
was added under a flow of argon, and the flask sealed and immediately
immersed in a preheated oil bath (1108C). The mixture was stirred for
1 h then allowed to reach room temperature. (ca. 20 min), filtered
through a pad of silica gel, and washed with AcOEt (3ꢄ4 mL) to sepa-
rate the catalyst. After removal of the solvent under reduced pressure,
the crude product was purified by column chromatography on silica gel.
G
ACHTUNGTRENNUNG
E
ACHTUNGTRENNUNG
0.125 mmol), and THF (40 mL) was added under argon. After stirring for
5 min at room temperature, HBF4 in water (40%, 50 mL, 0.3 mmol) was
added dropwise over 5 min, during which the yellow solid disappeared.
After stirring for 2 h at room temperature, the solution was concentrated
under vacuum. The light yellow solid was washed with diethyl ether
(97 mg, 93% yield). Crystals suitable for X-ray crystallography were ob-
tained by slow diffusion of diethyl ether into a solution in dichloroethane.
1H NMR (300 MHz, CD2Cl2): d=8.66 (d, J=5.9 Hz, 2H), 7.99 (t, J=
7.4 Hz, 2H), 7.65 (d, J=7.7 Hz, 2H), 7.44–7.56 (m, 6H), 7.29–7.33 (m,
12H), 7.16 (t, J=9.2 Hz, 4H), 4.76 (m, 2H), 4.34 (t, J=14.4 Hz, 2H),
À20.81 ppm (q, J=24.7 Hz, 1H); 31P NMR (121 MHz, CD2Cl2): d=
54.8 ppm (d, JP-Rh =120.5 Hz).
Procedure C: A dry, argon-flushed 1 mL Schlenk vessel with a Teflon
screw cap was charged with [{RhACHTNUTRGENN(UG COD)ACHUTNGTRENN(GUN m2-Cl)}2] (2.2 mg, 0.0044 mmol,
1.0 mol%), DPPMP (2.4 mg, 0.0088 mmol, 2 mol%), carboxylic acid
(0.44 mmol), and alkyne (0.66 mmol). Freshly distilled THF (0.7 mL) was
then added under a flow of argon and the Schlenk vessel was then sealed
and immediately immersed in a preheated oil bath (1108C). The mixture
was stirred for 16–24 h, allowed to reach room temperature (ca. 20 min),
filtered through a pad of silica gel, and washed with AcOEt (3ꢄ4 mL) to
separate the catalyst. After removal of the solvent under reduced pres-
sure, the crude product was analyzed by 1H NMR and GC and purified
by flash chromatography on silica gel.
[Rh
ACHTUNGTRENNUNG(DPPMP)2][HACHTUNGTRENNUNG
was charged with [Rh
N
ACHTUNGTRENNUNG
0.1 mmol), benzoic acid (25 mg, 0.2 mmol), and THF (3 mL). After stir-
ring for 1 h at 508C, the solvent was removed, and the residue was recrys-
tallized from diethyl ether and THF to yield 45 mg of [Rh
ACHTUNGTERNUN(NG DPPMP)2][H-
ACHTUNGTRENNUNG
phy were obtained by slow diffusion of diethyl ether into a solution in
THF. 1H NMR (300 MHz, CD2Cl2): d=15.02 (brs, 1H), 8.45 (d, J=
5.5 Hz, 2H), 8.04–8.08 (m, 4H), 7.81 (t, J=7.8 Hz, 2H), 7.49 (d, J=
7.9 Hz, 2H), 7.14–7.44 (m, 28H), 4.02 ppm (t, J=5.6 Hz, 4H); 13C NMR
(75 MHz, CD2Cl2): d=170.2, 160.9, 151.9, 139.0, 135.9, 133.1, 132.6, 133.1,
131.0, 130.1, 128.7, 128.0, 124.4, 124.0, 44.2 ppm; 31P NMR (121 MHz,
CD2Cl2): d=60.7 ppm (d, JP-Rh =168.9 Hz); MS (ESI-TOF): calcd for
[M]+ (C36H32N2P2Rh): 657.1090; found: 657.1101.
(Z)-1-(Benzoyloxy)-1-octene (8): Procedure A: AM-Z/AM-E/M=95/2/3,
yield: 99% (103 mg). Procedure B: AM-Z/AM-E/M=95/–/5, yield: 95%
(99 mg). Procedure C: AM-Z/AM-E/M=94/3/3, yield: 90% (94 mg). Pu-
rified by column chromatography on silica gel (eluent: hexanes/AcOEt
50/1, Rf =0.45); obtained as a colorless oil. 1H NMR (400 MHz, CDCl3):
d=8.10–8.13 (m, 2H), 7.57–7.62 (m, 1H), 7.45–7.51 (m, 2H), 7.27 (dt, J=
6.4, 1.5 Hz, 1H), 5.02 (td, J=7.5, 6.4 Hz, 1H), 2.30 (qd, J=7.3, 1.5 Hz,
2H), 1.28–1.50 (m, 8H), 0.86–0.92 ppm (m, 3H); 13C NMR (100 MHz,
CDCl3): d=163.6, 134.1, 133.3, 129.8, 129.5, 128.5, 114.9, 31.6, 29.1, 28.8,
24.6, 22.6, 14.1 ppm.
[Rh
ACHTUNGTRENNUNG(DPPMP)2]BF4: A dry, argon-flushed Schlenk tube was charged with
[Rh(COD)2]BF4 (122 mg, 0.3 mmol) and DPPMP (167 mg, 0.6 mmol),
ACHTUNGTRENNUNG
and THF (15 mL) was added. After stirring for 1 h at room temperature
and 30 min at 508C, the solvent was removed, and the residue was recrys-
tallized from THF. 1H NMR (300 MHz, CD2Cl2): d=8.49 (d, J=5.5 Hz,
2H), 7.86 (t, J=7.7 Hz, 2H), 7.51 (d, J=7.7 Hz, 2H), 7.16–7.41 (m,
22H), 4.07 ppm (t, J=5.7 Hz, 4H); 13C NMR (75 MHz, CD2Cl2): d=
152.1, 139.1, 133.2, 131.3, 128.9, 124.5, 124.2, 44.3 ppm; 31P NMR
(121 MHz, CD2Cl2): d=60.8 ppm (d, JP-Rh =168.5 Hz); MS (ESI-TOF):
calcd for [M]+ (C36H32N2P2Rh): 657.1090; found: 657.1092.
(Z)-1-(3-Acetoxybenzoyloxy)-1-octene (9): Procedure A: AM-Z/AM-E/
M=96/–/4 yield: 99% (129 mg). Procedure C: AM-Z/AM-E/M=95/–/5,
yield: 95% (105 mg). Purified by column chromatography on silica gel
(eluent: hexanes/AcOEt 2/1, Rf =0.74); obtained as
a yellow oil.
1H NMR (400 MHz, CDCl3): d=7.96–8.00 (m, 1H), 7.80–7.83 (m, 1H),
7.46–7.52 (m, 1H), 7.34 (ddd, J=8.1, 2.4, 1.1 Hz, 1H), 7.24 (dt, J=6.3,
1.6 Hz, 1H), 5.03 (td, J=7.5, 6.3 Hz, 1H), 2.33 (s, 3H), 2.28 (qd, J=7.3,
1.6 Hz, 2H), 1.26–1.49 ppm (m, 11H); 13C NMR (100 MHz, CDCl3): d=
169.0, 162.6, 150.7, 134.0, 131.0, 129.5, 127.2, 126.8, 123.0, 115.2, 31.6,
29.0, 28.8, 24.6, 22.5, 21.0, 14.0 ppm.
[{Rh
ACHTUNGTRENNUNG
charged with [Rh
N
ACHTUNGTRENNUNG
(29 mg, 0.24 mmol), and THF (4 mL) was added. After stirring for 1 h at
1008C the solvent was removed under vacuum and the residue recrystal-
lized from C2H4Cl2/hexane. 1H NMR (300 MHz, CD2Cl2): d=7.76–7.80
(m, 4H), 7.33–7.38 (m, 2H), 7.23–7.29 (m, 4H), 4.29 (s, 8H), 2.77–2.89
(m, 8H), 1.90 ppm (d, J=8.0 Hz, 8H); 13C NMR (75 MHz, CD2Cl2): d=
176.7, 134.9, 131.7, 129.9, 128.2, 81.6, 74.9, 31.5 ppm; MS: (EI, 70 eV): m/
z (%): 664 (0.5) [M]+, 332 (8), 286 (2), 210 (3), 208 (4), 122 (93), 108 (4),
(Z)-1-(2,4,6-Trimethoxybenzoyloxy)-1-octene (10): Procedure A: AM-Z/
AM-E/M 97/–/3, yield: 66% (96 mg). Procedure C: AM-Z/AM-E/M=
95/–/5, yield: 88% (128 mg). Purified by column chromatography on
silica gel (eluent: hexanes/AcOEt 3/1, Rf =0.38); obtained as a colorless
1
oil. H NMR (400 MHz, CDCl3): d=7.15 (dt, J=6.5, 1.5 Hz, 1H), 6.11 (s,
2H), 4.95 (td, J=7.5, 6.5 Hz, 1H), 3.82 (s, 3H), 3.81 (s, 6H), 2.16 (qd, J=
12074
ꢂ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2013, 19, 12067 – 12076