K. A. Vallianatou et al. / Tetrahedron Letters 54 (2013) 397–401
401
Popova, L. N.; Petrovskii, P. V.; Davankov, V. A.; Gavrilov, K. N. Russ. J. Coord.
Chem. 2007, 33, 656–660; (g) Gavrilov, K. N.; Maksimova, M. G.; Zheglov, S. V.;
Bondarev, O. G.; Benetsky, E. B.; Lyubimov, S. E.; Petrovskii, P. V.; Kabro, A. A.;
Hey-Hawkins, E.; Moiseev, S. K.; Kalinin, V. N.; Davankov, V. A. Eur. J. Org. Chem.
2007, 4940–4947.
[Rh(COD)2]BF4 (0.065 g, 0.16 mmol) in CH2Cl2 (2 mL) at 0 °C. The mixture was
stirred at this temperature for 30 min, and then for an additional 2.5 h at room
temperature. The resulting solution was evaporated under reduced pressure to
1 mL, and addition of hexane (10 mL) caused precipitation of a solid. The
supernatant was decanted, the solid was washed with hexane and Et2O, and
dried under vacuum, yielding a mixture of rhodium complexes 3 and 4 in a
molar ratio of 1.2:1 (0.090 g; 31% yield for 3 and 52% yield for 4) as a yellow–
orange solid, mp 199–204 °C (dec.). 1H NMR (CD2Cl2, 300.1 MHz): d 8.26–7.96,
7.62–7.51, 7.39–7.27, 7.13–7.07, 6.70–6.66 and 6.55–6.53 (m, 50H, Ar), 6.31–
6.09, 6.02–5.96, 5.92–5.85, 5.33–5.32 and 4.38 (m, 11H, COD-CH), 4.31, 4.22–
4.17, 4.10–4.08 and 3.96–3.92 (m, 6H, CH2N), 3.80–3.48 (m, 6H, CH2O), 3.17 (s,
3H, NCH3), 2.92 (s, 5H, NCH3), 2.35–2.16 and 2.03–1.90 (m, 22H, COD-CH2);
31P{1H} NMR (CD2Cl2, 121.5 MHz): d 126.50 (d, JRhP = 262.6 Hz) (3) and 123.27
(d, JRhP = 258.6 Hz) (4). HRMS (ESI+): calcd for C37H36NO3PRh [MꢁBF4]+ (3)
676.1482, found 676.1507; calcd for C66H60N2O6P2Rh [MꢁBF4]+ (4) 1141.2976,
found 1141.3027.
25. (a) Pàmies, O.; Diéguez, M.; Claver, C. J. Am. Chem. Soc. 2005, 127, 3646–3647;
(b) Diéguez, M.; Pàmies, O. Chem. Eur. J. 2008, 14, 3653–3669; (c) Mata, Y.;
Pámies, O.; Diéguez, M. Adv. Synth. Catal. 2009, 351, 3217–3234; (d) Mazuela,
J.; Paptchikhine, A.; Tolstoy, P.; Pàmies, O.; Diéguez, M.; Andersson, P. G. Chem.
Eur. J. 2010, 16, 620–638.
26. (a) Mata, Y.; Pàmies, O.; Diéguez, M. Chem. Eur. J. 2007, 13, 3296–3304; (b)
Mazuela, J.; Pàmies, O.; Diéguez, M. Chem. Eur. J. 2010, 16, 3434–3440.
27. (a) Escher, I. H.; Pfaltz, A. Tetrahedron 2000, 56, 2879–2888; (b) Hu, X.; Chen,
H.; Zhang, X. Angew. Chem., Int. Ed. 1999, 38, 3518–3521; (c) Arena, C. G.;
Calabrò, G.-P.; Franciò, G.; Faraone, F. Tetrahedron: Asymmetry 2000, 11, 2387–
2392; (d) Diéguez, M.; Ruiz, A.; Claver, C. Tetrahedron: Asymmetry 2001, 12,
2861–2866; (e) Mata, Y.; Diéguez, M.; Pàmies, O.; Biswas, K.; Woodward, S.
Tetrahedron: Asymmetry 2007, 18, 1613–1617; (f) Xie, Y.; Huang, H.; Mo, W.;
Fan, X.; Shen, Z.; Shen, Z.; Sun, N.; Hu, B.; Hu, X. Tetrahedron: Asymmetry 2009,
20, 1425–1432; (g) Chen, Y.-L.; Fröhlich, R.; Hoppe, D. Tetrahedron: Asymmetry
2009, 20, 1144–1149.
28. (a) Diéguez, M.; Mazuela, J.; Pàmies, O.; Verendel, J. J.; Andersson, P. G. Chem.
Commun. 2008, 3888–3890; (b) Mazuela, J.; Verendel, J. J.; Coll, M.; Schäffner,
B.; Börner, A.; Andersson, P. G.; Pàmies, O.; Diéguez, M. J. Am. Chem. Soc. 2009,
131, 12344–12353; (c) Mazuela, J.; Norrby, P.-O.; Andersson, P. G.; Pámies, O.;
Diéguez, M. J. Am. Chem. Soc. 2011, 133, 13634–13645.
29. Mazuela, J.; Paptchikhine, A.; Pàmies, O.; Andersson, P. G.; Diéguez, M. Chem.
Eur. J. 2010, 16, 4567–4576.
30. Goulioukina, N. S.; Bondarenko, G. N.; Bogdanov, A. V.; Gavrilov, K. N.;
Beletskaya, I. P. Eur. J. Org. Chem. 2009, 510–515.
Rh complex 4 was synthesized as described above by the reaction of ligand 2
(0.069 g, 0.15 mmol) and [Rh(COD)2]BF4 (0.030 g, 0.07 mmol) in CH2Cl2 (4 mL).
Complex 4 was obtained as a yellow–orange solid (0.078 g, 0.06 mmol, 86%),
mp 203–208 °C (dec.). 1H NMR (CD2Cl2, 599.8 MHz): d 8.16 (d, 3J = 8.8 Hz, 2H,
Ar), 8.09 (d, 3J = 8.2 Hz, 2H, Ar), 7.95 (d, 3J = 8.2 Hz, 2H, Ar), 7.82 (d, 3J = 8.9 Hz,
2H, Ar), 7.66 (d, 3J = 8.9 Hz, 2H, Ar), 7.59–7.52 (m, 4H, Ar), 7.36–7.27 (m, 8H,
Ar), 7.21 (d, 3J = 8.7 Hz, 2H, Ar), 7.11–7.08 (m, 4H, Ar), 6.68 (t, 3J = 7.5 Hz, 2H,
Ar), 6.54 (d, 3J = 8.0 Hz, 4H, Ar), 5.88 (br s, 2H) and 4.40 (m, 2H) (COD-CH), 4.09
(m, 2H) and 3.94 (m, 2H) (CH2N), 3.53–3.49 (m, 2H) and 3.46–3.41 (m, 2H)
(CH2O), 2.92 (s, 3H, NCH3), 2.35–2.18 and 2.02–1.98 (2 ꢂ m, 8H, COD-CH2);
13C{1H} NMR (CD2Cl2, 75.5 MHz): d 148.84–112.50 (Ar), 109.58–109.41 (m,
COD-CH), 68.38–68.23 (m, CH2N), 52.78–52.70 (m, CH2O), 39.62 (NCH3), 30.46
and 29.51 (COD-CH2); 31P{1H} NMR (CD2Cl2, 121.5 MHz):
d 123.35 (d,
JRhP = 258.4 Hz). HRMS (ESI+): calcd. for C66H60N2O6P2Rh [MꢁBF4]+
31. (a) Kostas, I. D.; Screttas, C. G. J. Organomet. Chem. 1999, 585, 1–6; (b) Kostas, I.
D. J. Chem. Res. (S) 1999, 630–631; (c) Kostas, I. D. J. Organomet. Chem. 2001,
626, 221–226; (d) Kostas, I. D. J. Organomet. Chem. 2001, 634, 90–98; (e) Kostas,
I. D.; Steele, B. R.; Terzis, A.; Amosova, S. V. Tetrahedron 2003, 59, 3467–3473;
(f) Kostas, I. D. Inorg. Chim. Acta 2003, 355, 424–427; (g) Kostas, I. D.; Steele, B.
R.; Andreadaki, F. J.; Potapov, V. A. Inorg. Chim. Acta 2004, 357, 2850–2854; (h)
Kostas, I. D.; Vallianatou, K. A.; Holz, J.; Börner, A. Appl. Organomet. Chem. 2005,
19, 1090–1095; (i) Tolis, E. I.; Vallianatou, K. A.; Andreadaki, F. J.; Kostas, I. D.
Appl. Organomet. Chem. 2006, 20, 335–337; (j) Vallianatou, K. A.; Kostas, I. D.;
Holz, J.; Börner, A. Tetrahedron Lett. 2006, 47, 7947–7950; (k) Kostas, I. D.;
Vallianatou, K. A.; Holz, J.; Börner, A. Tetrahedron Lett. 2008, 49, 331–334.
32. Ligand 2: A solution of [N-(2-hydroxyethyl)-N-methyl]aniline (1)31a (0.51 g,
3.38 mmol) and Et3N (2.4 mL) in toluene (8 mL) was added dropwise to a
solution of [(R)-(1,10-binaphthalene-2,20-diyl)]chlorophosphite (1.19 g,
3.39 mmol) in toluene (15 mL) at 0 °C. The reaction mixture was stirred at
this temperature for 2 h, then the temperature was increased slowly to room
temperature and the mixture was stirred overnight. The reaction mixture was
filtered through Celite, and dried under vacuum at 70 °C to yield 2 as a white
1141.2976, found 1141.2969.
Rh Complex 9 was prepared by the reaction of ligand 7 (0.056 g, 0.13 mmol) and
[Rh(COD)2]BF4 (0.054 g, 0.13 mmol) in CH2Cl2 (3 mL). Complex 9 was obtained
as an orange solid (0.079 g, 0.11 mmol, 85%), m.p. 215 °C (dec.). 1H NMR
(CD2Cl2, 300.1 MHz): d 8.65 (d, 3J = 5.4 Hz, 1H, -py CH), 8.15 (d, 3J = 9.0 Hz, 1H,
a
Ar), 8.00–7.97 (m, 3H, Ar), 7.91 (d, 3J = 8.1 Hz, 1H, Ar), 7.69–7.60 (m, 3H, Ar),
7.48–7.40 (m, 3H, Ar), 7.29–7.23 (m, 4H, Ar), 6.02–5.94 (m, 1H, CH2O), 5.61–
5.50 (m, 2H, COD-CH trans to P), 5.28–5.16 (m, 1H, CH2O), 4.41–4.39 (m, 1H)
and 3.40–3.36 (m, 1H) (COD-CH trans to N), 2.69–2.58, 2.50–2.38, 2.30–2.11
and 2.08–1.89 (4 ꢂ m, 8H, COD-CH2); 13C{1H} NMR (CD2Cl2, 75.5 MHz): d
3
155.03 (d, JCP = 5.1 Hz,
a
-py C), 153.15 (
a
-py CH), 147.21–120.79 (Ar), 118.18
1
2
1
2
(dd, JCRh = 14.6 Hz, JCP = 5.5 Hz) and 115.74 (dd, JCRh = 11.8 Hz, JCP = 4.8 Hz)
(COD-CH trans to P), 81.53 (d, JCRh = 11.7 Hz) and 78.95 (d, JCRh = 10.3 Hz)
(COD-CH trans to N), 71.42 (d, JCP = 10.4 Hz, CH2O), 35.15 (d, JCRh = 3.2 Hz),
30.59, 29.23 and 26.32 (COD-CH2); 31P{1H} NMR (CD2Cl2, 121.5 MHz): d 134.02
(d, JRhP = 255.5 Hz). HRMS (ESI+): calcd for C34H30NO3PRh [MꢁBF4]+ 634.1013,
found 634.1006.
1
1
2
2
Rh Complex 10 was synthesized by the reaction of ligand 8 (0.050 g, 0.11 mmol)
and [Rh(COD)2]BF4 (0.046 g, 0.11 mmol) in CH2Cl2 (3 mL). Complex 10 was
obtained as an orange solid (0.062 g, 0.12 mmol, 76%), mp 230 °C (dec.). 1H
solid (1.26 g, 2.71 mmol, 80%), mp 107–108 °C. ½a D20
ꢀ
ꢁ383.3 (c 0.84, CHCl3). 1
H
NMR (CDCl3, 599.8 MHz): d 7.89 (d, 3J = 9.0 Hz, 1H, Ar), 7.84 (d, 3J = 8.4 Hz, 1H,
Ar), 7.81 (d, 3J = 7.8 Hz, 1H, Ar), 7.73 (d, 3J = 8.4 Hz, 1H, Ar), 7.40–7.09 (m, 10H,
Ar), 6.63 (t, 3J = 7.2 Hz, 1H, Ar), 6.55 (d, 3J = 8.1 Hz, 2H, Ar), 4.00–3.95 (m, 1H,
CH2N), 3.83–3.78 (m, 1H, CH2N), 3.48–3.38 (m, 2H, CH2O), 2.85 (s, 3H, NCH3);
NMR (CD2Cl2, 300.1 MHz):
d a-py CH), 8.30 (d,
8.78 (d, 3J = 5.7 Hz, 1H,
3J = 8.7 Hz, 1H, Ar), 8.09–7.89 (m, 5H, Ar), 7.66–7.28 (m, 9H, Ar), 5.45 (m, 1H,
COD-CH trans to P), 5.32–5.18 (m, 2H, COD-CH trans to P, and CH2–py), 5.11–
5.07 (m, 1H, CH2O), 4.47–4.34 (m, 2H, CH2O and COD-CH trans to N), 3.68 (dd,
J = 14.1 Hz, J = 3.9 Hz, 1H, CH2–py), 3.18–3.13 (m, 1H, COD-CH trans to N),
2.79–2.65, 2.51–2.46, 2.35–2.22 and 2.10–1.97 (4 ꢂ m, 8H, COD-CH2); 13C{1H}
13C{1H} NMR (CDCl3, 75.5 MHz): d 148.82–112.19 (Ar), 62.4 (d, JCP = 3.5 Hz,
3
2
CH2N), 53.2 (d, JCP = 3.9 Hz, CH2O), 39.06 (s, NCH3); 31P{1H} NMR (CDCl3,
242.8 MHz): d 140.39. HRMS (ESI+): calcd for C29H25NO3P [M+H]+ 466.1567,
found 466.1572.
NMR (CD2Cl2, 75.5 MHz): d 159.29 (a-py C), 151.44 (a-py CH), 147.14–120.63
1 2 1
Ligand 723 was synthesized as described for
2
by the reaction of 2-
(Ar), 115.82 (dd, JCRh = 15.3 Hz, JCP = 5.7 Hz) and 112.09 (dd, JCRh = 12.4 Hz,
1
(hydroxymethyl)-pyridine
(5)
(0.18 g,
1.65 mmol)
and
[(R)-(1,10-
2JCP = 5.1 Hz) (COD-CH trans to P), 80.31 (d, JCRh = 11.3 Hz) and 79.58 (d,
binaphthalene-2,20-diyl)]chlorophosphite (0.58 g, 1.65 mmol) in toluene
1JCRh = 11.5 Hz) (COD-CH trans to N), 66.65 (CH2O), 41.31 (d, 3JCP = 8.2 Hz, CH2–
2
(12 mL)/Et3N (1.2 mL). Compound 7 was obtained as a white solid (0.60 g,
py), 34.60 (d, JCRh = 2.3 Hz), 30.75, 29.71 and 26.72 (COD-CH2); 31P{1H} NMR
1.42 mmol, 86%), mp 120 °C. ½a D20
ꢀ
ꢁ435.0 (c 0.70, CDCl3). 1H NMR (CDCl3,
(CD2Cl2, 121.5 MHz): d
124.21 (d, JRhP = 252.8 Hz). HRMS (ESI+): calcd for
599.8 MHz): d 8.42 (d, 3J = 4.7 Hz, 1H,
a
-py CH), 7.91–7.77 (m, 4H, Ar), 7.63–
C
35H32NO3PRh [MꢁBF4]+ 648.1169, found 648.1152.
7.57 (m, 1H, Ar), 7.46–6.86 (m, 10H, Ar), 5.06–4.99 (m, 1H, CH2O), 4.84–4.77
34. Anderson, M. P.; Casalnuovo, A. L.; Johnson, B. J.; Mattson, B. M.; Mueting, A.
M.; Pignolet, L. H. Inorg. Chem. 1988, 27, 1649–1658.
(m, 1H, CH2O); 13C{1H} NMR (CDCl3, 75.5 MHz): d 157.21 (d, 3JCP = 4.3 Hz,
a-py
C), 149.01 (
a
-py CH), 148.57–121.09 (Ar), 66.88 (d, 2JCP = 4.7 Hz, CH2O); 31P{1H}
35. Brancatelli, G.; Drommi, D.; Bruno, G.; Faraone, F. Inorg. Chem. Commun. 2010,
13, 215–219.
36. Borns, S.; Kadyrov, R.; Heller, D.; Baumann, W.; Spannenberg, A.; Kempe, R.;
Holz, J.; Börner, A. Eur. J. Inorg. Chem. 1998, 1291–1295.
NMR (CDCl3, 121.5 MHz): d 136.05. HRMS (ESI+): calcd for C26H19NO3P [M+H]+
424.1097, found 424.1088.
Ligand 8 was synthesized by the reaction of 2-(2-hydroxyethyl)-pyridine (6)
(0.18 g, 1.46 mmol) and [(R)-(1,10-binaphthalene-2,20-diyl)]chlorophosphite
37. In a typical experiment, a solution of the prochiral olefin (0.1 mmol), the ligand
(0.001 mmol) and [Rh(COD)2]BF4 (0.001 mmol) in CH2Cl2 (0.3 mL) was
prepared under a nitrogen atmosphere in a glove box and then transferred
into an autoclave, which was then closed and pressurized with H2 (50 bar).
After 4 h at room temperature, the pressure was carefully released, hexane
(2 mL) was added and the mixture was filtered through silica (hexane/
EtOAc = 1:1). All solvents were removed under vacuum, the conversions were
determined by achiral GC, and the ee values and configurations were
determined by chiral GC or HPLC by comparison with the retention times of
known enantiomers.
(0.50 g, 1.43 mmol) in toluene (12 mL)/Et3N (1.0 mL). Compound
8 was
obtained as a white solid (0.45 g, 1.03 mmol, 72%), mp 59 °C (dec.). ½a D20
ꢀ
ꢁ414.8 (c 0.98, CHCl3). 1H NMR (CDCl3, 300.1 MHz): d 8.46 (d, 3J = 4.2 Hz, 1H,
a
-py CH), 7.91–7.80 (m, 4H, Ar), 7.56–7.50 (m, 1H, Ar), 7.40–7.11 (m, 10H, Ar),
4.34–4.24 (m, 1H, CH2O), 4.17–4.07 (m, 1H, CH2O), 3.04 (t, 3J = 6.3 Hz, 2H, CH2–
py); 13C{1H} NMR (CDCl3, 75.5 MHz): d 157.89 (
a
-py C), 149.33 (
a-py CH),
2
3
148.56–121.58 (Ar), 64.20 (d, JCP = 7.4 Hz, CH2O), 39.67 (d, JCP = 4.2 Hz, CH2–
py); 31P{1H} NMR (CDCl3, 121.5 MHz):
d
139.37. HRMS (ESI+): calcd for
C27H21NO3P [M+H]+ 438.1254, found 438.1233.
33. Reaction of 2 with [Rh(COD)2]BF4 in a ratio of 1:1: A solution of ligand 2 (0.075 g,
0.16 mmol) in CH2Cl2 (3 mL) was added dropwise to a dark red solution of