ars.els-cdn.com · web viewnuclear magnetic resonance spectra (1h nmr and 13c nmr) were obtained on...
TRANSCRIPT
Supporting Information for:
Asymmetric Michael Addition of Malonates to Unsaturated
Ketones Catalyzed by Rare Earth Metal Complexes Bearing
Phenoxy Functionalized Chiral Diphenylprolinolate Ligands
Qinqin Qian, Wenguo Zhu, Chengrong Lu, Bei Zhao*and Yingming Yao*
Table of contentsPage
General methods S-1Crystallographic data for complex 3 S-2X-ray structures of complex 3 S-3General procedure for the asymmetric Michael addition S-31H NMR, 13C NMR spectra and HPLC chromatograms for target adducts S-41H NMR, 13C NMR spectra for complexes 2-4 S-20
General methodsAll reagents are commercially available, reagent grade, and used as received unless otherwise
noted. Experiments involving air and water sensitive components were performed in glovebox or using the standard Schlenk techniques. Hexane, toluene, and THF were degassed and distilled from sodium benzophenone ketyl before use, the other solvent were distilled after treatment with calcium hydride. Analytical thin layer chromatography (TLC) was performed using F254 pre-coated silica gel plate (0.2 mm thickness). After elution, plates were detected using UV radiation (254 nm) on a UV lamp.
Nuclear magnetic resonance spectra (1H NMR and 13C NMR) were obtained on a Bruker AV-400 apparatus (CDCl3 as solvent). Chemical shifts for 1H NMR spectra were reported in ppm from tetramethylsilane with the solvent resonance as the internal standard (CDCl3, δ = 7.26). Spectra were reported as follows: chemical shift (δ ppm), multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet), coupling constants (Hz), integration and assignment. Carbon nuclear magnetic resonance spectra (13C NMR) are reported as δ in units of parts per million (ppm) downfield from SiMe4 (δ 0.0) and relative to the signal of chloroform-d (δ 77.0, triplet).
High Resolution Mass (HRMS) spectra were obtained using Bruker ESI-TOF.Enantiomeric excesses (ee) were determined by HPLC analysis (Shimadzu LC-20A) using the
corresponding commercial chiral column as stated in the experimental procedures at 23 oC. Optical rotations were reported as follows: [α] D
T (c g/100 mL, in solvent).Suitable single crystals of complex and 3 were sealed in a thin-walled glass capillary for
determining the single-crystal structure. Intensity data were collected with a Rigaku Mercury CCD area detector in ω scan mode using Mo-Kα radiation (λ = 0.71075 Å). The diffracted intensities were corrected for Lorentz polarization effects and empirical absorption corrections. Details of the intensity data collection and crystal data are given in Table 1. All the non-hydrogen atoms were refined anisotropically. All the H atoms were held stationary and included in the structure factor calculation in the final stage of full-matrix least-squares refinement. The structures were solved and refined using SHELEXL-97 programs.
Rare earth metal analysis was performed by EDTA titration with a xylenol orange indicator and a hexamine buffer[1]. Carbon, hydrogen and nitrogen analyses were performed by direct combustion with a Carlo-Erba EA-1110 instrument.
S-1
Experimental section:General Procedure for the Preparation of the Rare Earth Metal Complexes 1-4:
Table 1 Crystallographic Data for Complex 3
Compound 3
Formula C64H79N2O4Sc
fw 985.25
Crystal system orthorhombic
Crystal size/mm 1.40 × 1.10 × 1.00
Space group P 21 21 21
a/Å 17.887(3)
b/Å 20.044(3)
c/Å 21.041(4)
V/Å3 7544(2)
Z 4
Dcalcd/g cm-3 0.868
/mm-1 0.133
F(000) 2120
max/ 27.50
Collected 23496
Unique reflns 9293Obsd reflns[I 2.0(I)] 6804
No. of variables 326
GOF 1.538
R 0.1848
wR 0.4301
Rint 0.059Largest diff. peak,
hole/e Å-3 1.16, -0.38
S-2
X-Ray Structures of Complex 3 and selected bond lengths and bond anglesCrystals of complex 3 suitable for X-ray diffraction were obtained in toluene at room temperature. The definitive structure is shown in Figure 1, and the corresponding selected bond lengths and angles are provided in the figure captions.
Figure 1. Molecular structure of 3 showing 20% probability ellipsoids. Hydrogen atoms are omitted for clarity.
General Procedure for the asymmetric Michael addition of malonates to -Unsaturated Ketones
The procedures for asymmetric Michael addition of -unsaturated ketones catalyzed by complexes 1 to 4 are similar, and a typical procedure is given below. A 10 mL Schlenk flask was charged with a mixture of chalcone (0.3 mmol), catalyst (0.03 mmol), molecular sieve 3Å (60 mg, 30 mg/mmol of starting material), and 1 mL DCM. After stirring for about 30 min. at room temperature, the malonate (0.36 mmol) was added in one portion. The reaction system was maintained at 25 oC for 50 h, quenched by adding water, the reaction mixture was purified by flash chromatography (petroleum ether : ethyl acetate = 20 : 1) on silica gel to afford the desired product. The enantiomeric excess of the product was determined by chiral stationary-phase HPLC analysis.
S-3
The 1H and 13C spectra and HPLC spectrum of compound 7c
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5
3.00
2.93
6.11
1.02
1.04
1.05
1.05
1.04
1.01
0.95
4.28
2.10
1.15
1.99
0.96
000.97
561.03
141.04
701.23
091.24
663.39
483.41
873.43
613.46
003.50
553.51
593.54
673.55
723.75
533.78
014.14
704.15
744.77
164.78
734.80
305.05
565.07
135.08
695.10
26
7.13
007.14
777.16
457.20
177.22
047.23
957.24
717.26
107.39
477.41
347.43
287.50
097.51
967.53
777.87
877.89
89
-100102030405060708090100110120130140150160170180190200210
21.42
21.47
21.68
21.81
40.89
43.08
58.01
68.98
69.38
127.19
128.24
128.45
128.51
128.66
133.10
137.01
140.60
167.39
168.09
197.77
S-4
S-5
The 1H and 13C spectra and HPLC spectrum of compound 7d
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0
2.96
2.90
5.90
0.98
1.02
0.98
2.88
1.11
1.00
1.08
1.87
0.90
4.20
2.13
1.00
501.02
071.07
651.09
221.27
931.28
223.41
273.43
693.49
553.50
593.53
583.80
123.82
613.89
214.17
894.18
934.81
614.83
184.84
745.10
535.12
105.13
666.92
576.94
777.24
527.26
477.29
067.31
35
7.92
177.94
39
-100102030405060708090100110120130140150160170180190200210
20.80
20.85
21.06
21.19
40.53
42.16
54.95
57.46
68.32
68.73
113.17
126.53
127.79
127.89
129.92
140.02
162.88
166.80
167.51
195.68
S-6
The 1H and 13C spectra and HPLC spectrum of compound 7e
-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5
3.00
2.95
5.98
1.00
1.02
0.99
1.04
1.12
0.98
1.33
3.80
2.13
2.00
0.95
850.97
411.02
971.04
521.22
951.24
503.37
423.39
853.49
133.50
123.53
193.54
203.73
683.76
154.10
404.11
394.76
854.78
404.79
964.81
485.05
225.06
785.08
345.09
897.15
537.16
637.22
087.23
127.37
677.39
787.82
037.84
13
-100102030405060708090100110120130140150160170180190200210
21.41
21.45
21.66
21.80
40.96
43.12
57.88
69.04
69.47
127.32
128.42
128.51
128.98
129.70
135.21
139.54
140.27
167.30
168.08
196.69
S-7
The 1H and 13C spectra and HPLC spectrum of compound 7f
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
3.00
3.15
5.89
1.03
1.02
1.02
1.05
1.03
1.00
1.08
4.04
2.03
2.03
0.97
320.98
881.04
571.06
131.24
461.26
023.34
953.37
383.39
043.41
463.50
773.51
793.54
853.55
873.76
143.78
624.12
554.13
584.76
934.78
494.80
064.81
624.83
195.06
925.08
485.10
055.11
61
7.17
317.23
517.24
097.24
837.54
917.57
047.75
667.77
80
-100102030405060708090100110120130140150160170180190200210
21.41
21.45
21.66
21.80
40.97
43.09
57.89
69.03
69.44
127.31
128.28
128.43
128.51
129.81
131.97
135.68
140.32
167.29
168.07
196.87
S-8
The 1H and 13C spectra and HPLC spectrum of compound 7g
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
3.00
3.14
6.29
1.02
1.02
1.03
1.04
1.04
1.02
1.01
4.21
2.05
2.04
0.97
320.98
891.04
941.06
501.24
681.26
253.41
293.43
713.45
403.47
823.58
813.59
823.62
923.63
933.78
033.80
514.14
674.15
694.78
934.80
504.82
074.83
635.07
615.09
175.10
745.12
30
7.16
837.17
677.18
407.21
827.23
837.67
187.69
257.99
018.01
04
-100102030405060708090100110120130140150160170180190200210
21.31
21.36
21.56
21.70
40.86
43.38
57.76
68.99
69.42
119.61
122.32
125.03
125.65
125.67
127.31
127.74
128.07
128.37
128.49
128.53
128.94
133.74
134.07
134.40
139.57
140.20
167.20
168.01
196.92
S-9
S-10
The 1H and 13C spectra and HPLC spectrum of compound 7h
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5
3.23
2.65
6.50
0.95
0.98
3.52
1.09
0.92
1.00
1.72
1.87
1.75
1.14
1.90
0.00
040.07
040.98
521.00
081.05
131.06
691.23
151.23
831.24
711.25
423.36
323.37
953.40
403.47
883.48
893.51
963.52
983.70
943.73
104.09
124.10
104.78
464.80
034.81
595.04
175.05
735.07
305.08
876.74
586.76
747.15
157.17
317.39
807.41
657.43
607.50
307.52
157.53
967.88
207.90
01
-100102030405060708090100110120130140150160170180190200210
20.86
20.91
21.07
21.21
39.62
42.67
54.67
57.60
68.32
68.72
113.20
127.64
128.04
128.90
131.91
132.46
136.41
158.00
166.82
167.53
197.35
S-11
The 1H and 13C spectra and HPLC spectrum of compound 7i
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5
3.00
2.93
6.22
2.13
1.06
1.09
1.08
1.11
4.87
1.25
3.99
2.07
0.88
290.89
860.99
191.00
761.22
871.23
421.24
441.24
983.51
813.55
983.58
273.59
033.60
173.63
203.86
333.88
794.30
724.31
854.33
084.34
224.35
444.72
444.74
014.75
575.05
405.06
975.08
535.10
10
7.39
117.40
337.42
357.44
847.49
347.51
197.53
047.68
237.72
447.74
507.88
167.89
95
-100102030405060708090100110120130140150160170180190200210
21.39
21.49
21.70
21.82
40.91
43.03
58.04
69.03
69.45
125.78
126.04
126.57
127.41
127.67
127.93
128.17
128.25
128.67
132.70
133.14
133.38
136.98
138.20
167.38
168.10
197.69
S-12
The 1H and 13C spectra and HPLC spectrum of compound 7j
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5
3.00
3.00
6.07
1.13
1.10
1.18
1.14
1.23
1.10
1.99
2.05
2.05
1.05
1.92
0.98
701.00
271.05
121.06
691.22
941.23
791.24
501.25
35
3.35
273.37
733.39
413.41
873.49
753.50
753.53
883.54
893.71
293.73
774.11
704.13
174.14
174.77
304.78
874.80
434.82
005.04
235.05
805.07
365.08
935.10
496.89
536.91
707.21
507.22
847.23
677.25
017.40
597.42
447.44
407.51
527.53
367.55
217.87
607.89
39
-100102030405060708090100110120130140150160170180190200210
21.47
21.51
21.68
21.82
40.20
43.10
57.99
69.12
69.50
115.19
115.40
128.22
128.73
130.09
130.16
133.25
136.89
167.29
167.93
197.65
S-13
The 1H and 13C spectra and HPLC spectrum of compound 7k
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5
3.00
2.97
6.06
1.12
1.12
1.09
1.19
1.22
1.15
3.86
2.05
1.25
2.05
0.99
971.01
541.06
031.07
591.22
901.23
701.24
451.25
263.36
553.39
013.40
733.43
193.49
823.50
823.54
003.55
003.71
013.73
474.12
444.13
44
4.78
194.79
754.81
324.82
894.84
455.04
015.05
575.07
155.08
715.10
287.20
757.40
947.42
807.44
777.52
027.53
867.55
697.87
467.87
797.89
59
-100102030405060708090100110120130140150160170180190200210
21.45
21.49
21.65
21.79
40.20
42.83
57.74
69.17
69.53
128.19
128.59
128.72
129.94
132.93
133.27
136.81
139.19
167.20
167.84
197.46
S-14
The 1H and 13C spectra and HPLC spectrum of compound 7l
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5
3.00
3.00
6.05
1.02
1.04
1.02
1.04
1.05
1.02
3.98
1.11
2.00
2.01
1.01
601.03
161.07
151.08
711.23
471.24
101.25
031.25
663.46
023.48
453.50
303.52
743.57
113.58
113.61
393.62
403.77
793.80
214.26
774.27
764.79
754.81
314.82
884.84
445.05
125.06
685.08
255.09
825.11
38
7.41
777.43
647.45
607.47
767.49
957.53
497.55
357.57
197.87
427.89
218.10
488.12
67
-100102030405060708090100110120130140150160170180190200210
21.51
21.65
21.80
40.41
42.44
57.23
69.52
69.84
123.66
128.15
128.84
129.63
133.56
136.53
147.07
148.64
166.94
167.50
196.94
S-15
The 1H and 13C spectra and HPLC spectrum of compound 7m
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.05.96
2.93
3.00
1.99
0.98
0.98
0.99
0.99
2.01
1.99
2.01
1.03
1.98
1.04
271.06
041.07
671.17
181.18
751.22
611.24
17
3.58
543.61
493.62
723.64
473.68
684.03
704.06
004.62
634.83
784.85
354.86
915.02
825.04
395.05
95
7.07
517.09
357.11
767.14
107.15
947.29
037.31
357.31
917.34
257.38
677.40
517.42
477.49
077.50
917.52
487.52
767.91
287.93
07
-100102030405060708090100110120130140150160170180190200210
21.33
21.40
21.58
21.66
37.53
40.85
55.68
69.09
69.28
126.77
128.16
128.25
128.58
129.71
130.04
133.09
134.22
136.81
137.92
167.31
167.90
197.56
S-16
The 1H and 13C spectra and HPLC spectrum of compound 7n
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
3.15
2.96
6.18
1.06
1.09
3.00
1.04
1.05
1.09
1.06
1.99
2.03
2.01
1.09
2.01
0.93
790.95
361.00
611.02
171.22
801.24
363.41
213.42
173.45
243.46
193.58
523.60
983.62
553.65
003.79
564.12
974.15
564.25
864.27
414.28
374.73
114.74
684.76
255.05
285.06
855.08
42
6.76
186.78
096.79
707.11
057.13
007.14
937.38
577.40
417.42
357.48
577.50
417.52
257.89
397.91
17
-100102030405060708090100110120130140150160170180190200210
21.38
21.47
21.67
21.81
38.44
41.11
55.33
55.53
68.61
69.08
110.91
120.42
127.78
128.25
128.42
128.52
131.19
132.82
137.24
157.68
167.78
168.55
198.50
S-17
S-18
The 1H and 13C spectra and HPLC spectrum of compound 7o
-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.5
3.00
3.04
6.67
2.19
1.12
1.10
1.12
1.15
1.09
2.05
3.45
0.84
1.09
0.96
030.97
591.02
271.03
831.22
981.23
561.24
541.25
133.30
533.32
283.74
363.76
894.10
654.11
414.12
404.13
174.76
604.78
165.05
235.06
795.08
366.46
486.46
956.47
37
7.13
537.14
427.16
217.19
857.21
797.23
587.25
037.26
737.27
177.51
297.51
55
-100102030405060708090100110120130140150160170180190200210
21.42
21.45
21.67
21.80
40.79
42.89
57.92
68.98
69.40
112.30
117.31
127.24
128.45
128.50
140.36
146.36
152.76
167.30
167.96
186.76
S-19
The 1H and 13C spectra and HPLC spectrum of compound 7p
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
3.00
3.10
6.11
1.07
1.14
1.06
1.09
1.06
1.06
1.01
1.07
3.45
0.38
0.98
1.01
0.96
160.97
721.02
441.04
011.23
251.23
701.24
811.25
273.30
293.32
713.34
243.36
663.42
353.43
403.46
293.47
343.75
843.78
344.12
034.13
084.78
435.07
36
7.07
907.16
777.20
327.22
267.24
867.26
987.56
617.57
847.72
397.73
33
-100102030405060708090100110120130140150160170180190200210
21.41
21.45
21.67
21.80
41.29
43.79
57.81
69.02
69.46
127.29
128.19
128.46
128.48
132.23
133.76
140.21
144.32
167.30
168.03
190.66
S-20
The 1H and 13C spectra and HPLC spectrum of compound 7q
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
3.00
3.06
6.29
0.95
0.96
0.99
0.98
0.98
0.99
8.06
1.00
0.91
150.92
721.01
941.03
501.23
411.24
981.25
651.27
223.59
553.60
593.63
863.64
903.67
253.69
933.81
723.84
233.86
033.88
544.05
494.06
524.08
084.09
134.10
674.72
714.74
274.75
844.77
415.05
015.06
575.08
145.09
717.11
427.12
507.13
197.14
507.14
967.16
347.17
827.19
727.21
487.23
807.25
097.25
557.25
987.26
697.27
807.28
527.29
088.10
288.11
90
-100102030405060708090100110120130140150160170180190200210
21.33
21.42
21.62
21.79
40.96
47.37
58.03
68.83
69.37
125.40
126.83
127.14
127.78
128.33
128.65
140.36
140.53
146.76
167.20
167.70
195.54
S-21
The 1H and 13C spectra and HPLC spectrum of compound 7r
-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0
3.00
6.06
2.94
0.99
1.00
1.99
0.99
3.06
2.15
2.00
3.02
1.08
2.01
1.98
0.93
760.95
321.00
491.01
591.02
041.03
141.09
601.11
174.21
584.23
684.56
704.58
864.61
024.76
814.78
384.79
944.81
514.83
074.84
354.85
914.87
474.89
04
6.39
716.41
937.02
567.04
287.05
477.07
357.09
027.25
787.27
687.29
647.33
967.35
697.39
147.40
987.42
977.49
987.51
837.72
547.72
847.74
678.00
268.02
09
-100102030405060708090100110120130140150160170180190200210
21.36
21.41
21.50
21.53
45.67
55.23
59.39
69.09
69.41
127.38
128.05
128.59
128.63
128.95
128.98
130.36
133.20
133.65
136.71
137.13
137.45
168.01
168.20
194.83
195.11
S-22
S-23
The 1H and 13C spectra of
L1Y(L1H) (2)
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.012
.14
15.07
9.07
4.11
2.11
2.41
1.84
2.24
2.31
4.04
0.72
1.32
4.07
9.38
1.23
3.09
2.00
3.28
1.28
1.36
1.44
1.82
2.01
2.36
2.64
2.81
3.14
3.71
4.26
6.77
6.85
7.12
7.17
7.22
7.24
7.26
7.28
7.52
7.72
7.78
5101520253035404550556065707580859095
15.4
20.6
24.4
25.7
28.7
29.5
29.6
30.1
30.2
31.8
32.0
34.0
34.2
35.0
35.1
35.2
51.1
53.5
55.3
61.8
62.0
66.0
67.2
68.1
72.8
76.3
77.4
79.9
81.6
82.4
S-24
S-25
The 1H and 13C spectra of L1Sc(L1H) (3)
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5
28.91
2.78
10.30
6.20
3.43
1.33
1.16
14.48
9.75
1.00
1.22
231.38
011.42
591.74
702.07
15
2.64
982.85
89
3.67
193.89
64
4.65
21
5.41
30
6.69
046.82
477.18
40
7.74
057.94
91
9.38
89
0102030405060708090100110120130140150160170180190200210220230
29.6
30.4
31.8
32.0
34.0
35.0
35.5
53.0
55.3
62.0
72.8
77.4
79.7
79.9
82.2
82.4
83.3
122.3
122.5
122.8
123.4
124.1
124.3
124.8
125.5
125.9
126.1
126.7
126.8
127.1
127.6
127.8
127.9
128.3
128.3
128.4
128.6
129.0
135.1
135.9
136.8
138.9
142.7
145.2
145.9
146.2
152.5
153.5
160.2
161.8
S-26
The 1H and 13C spectra of L2Sc(L2H) (4)
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0
2.05
6.29
17.36
2.14
2.17
3.34
2.80
0.52
0.55
2.82
0.79
0.73
1.20
1.07
29.42
5.73
3.32
1.68
1.00
1.12
881.36
241.59
651.64
041.93
522.15
892.25
432.49
362.62
403.00
373.29
183.73
123.88
90
6.44
716.63
246.73
217.03
027.37
887.46
937.62
307.99
83
8.85
62
-100102030405060708090100110120130140150160170180190200210220230
23.2
24.2
26.7
28.5
29.3
29.5
29.7
29.8
30.7
30.9
31.3
31.5
42.1
42.3
42.5
42.6
43.4
55.0
72.1
81.9
119.8
124.0
124.5
124.7
124.8
125.1
125.4
125.4
125.5
125.8
125.9
126.1
126.6
126.7
126.8
126.9
126.9
127.2
127.6
127.7
127.8
127.9
128.0
128.1
128.2
128.3
128.8
152.1
152.2
152.3
Reference:[1] Atwood, J. L.; Hunter, W. E.; Wayda, A. L.; Evans, W. J. Inorg. Chem. 1981, 20, 4115.
S-27