Fast, solvent-free, highly enantioselective three-component coupling of aldehydes, alkynes, and amines catalysed by the copper(II)pybox complex under high-vibration ball-milling

Article abstract of DOI:10.1039/c5gc00079c

Chiral propargylamines were synthesized in good to excellent yields with high enantioselectivity via Cu(OTf)₂/Ph-Pybox catalysed, solvent-free three-component asymmetric coupling of aldehydes, alkynes and amines by ball-milling within 60 minute

Full text of DOI:10.1039/c5gc00079c

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Green Chemistry
Green Chemistry
RSCPu b lish in g
View Article Online
DOI: 10.1039/C5GC00079C
COMMUNICATION
Fast, Solvent-Free, Highly Enantioselective Three-
Component Coupling of Aldehydes, Alkynes, and
Amines Catalysed by Copper(II)pybox Complex under
High-Vibration Ball-Milling
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Chiral propargylamines were synthesized in good to excellent
yields with high enantioselectivity via Cu(OTf)2/Ph-Pybox
catalysed solvent-free three-component asymmetric coupling
of aldehydes, alkynes and amines by ball-milling within 60
minutes. The catalytic system can be reused several times
without losing activity.
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Electronic Supplementary Information (ESI) available: experimental
procedures, results of extractant screening and the recyclability tests, and
full characterization of compounds. See DOI: 10.1039/c000000x/
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This journal is © The Royal Society of Chemistry 2015
Green Chem., 2015, 00, 1-4 | 1

Green Chemistry
Page 2 of 5
Green Chemistry
COMMUNICATION
Table 1 Catalyst screening for the A3 reaction. a
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a Unless otherwise mentioned, the reactions were performed with 1a (106
mg, 1.0 mmol), 2a (112 mg, 1.2 mmol), 3a (153 mg, 1.5 mmol), Catalyst
(10 mol%), Ligand (10 mol%), Silica gel (chromatography grade, 0.6 g)
and stainless steel balls (1.5cm*2) in a stainless-steel jar under ball-milling
at 30Hz. Isolated yield based on
reaction mixture. The reactions were performed with
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Determined by HPLC analysis of
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(chromatography grade, 0.6 g) in a stainless-steel jar under ball-milling at
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30Hz. copper balls (1.5cm*2) were used. Not detected. g Catalyst (7
mol%), Ligand (7 mol%) were used. h Catalyst (5 mol%), Ligand (5 mol%)
were used.
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Entry Freq.(Hz)
Additives (g)
Silica gel (0.6)
β-dextrin (0.8)
γ-Al2O3 (2.0)
NaCl (0.8)
NaCl (2.0)
NaSO4 (2.0)
CaCl2 (2.0)
Silica gel (0.6)
Silica gel (0.8)
Silica gel (1.0)
Silica gel (0.8)
Silica gel (0.8)
Silica gel (0.8)
t
(min)
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All the reactions were performed with 1a (106 mg, 1.0 mmol), 2a (112
mg, 1.2 mmol), 3a (153 mg, 1.5 mmol), Cu(OTf)2 (36 mg, 0.1 mmol), L1
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. c Determined by HPLC analysis of reaction
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2 | Green Chem., 2015, 00, 1-4
This journal is © The Royal Society of Chemistry 2015

Page 3 of 5
Green Chemistry
Table 3 Investigation of substrate scope. a
View Article Online
DOI: 10.1039/C5GC00079C
,
d
No.
1
2
3
4
5
6
7
8
Ar1
C6H5
Ar2
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
R
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
Product
4a
4b
4c
4d
4e
Time (min)
30
%yield b
99
99
99
97
97
94
99
99
96
99
95
93
99
94
92
90
94
99
99
93
99
90
92
%
ee c
99
98
97
98
96
89
99
99
85
83
88
97
99
90
99
97
95
99
98
88
95
88
88
4-MeC6H4
3,4-Me2C6H4
4-FC6H4
4-ClC6H4
4-BrC6H4
3-MeC6H4
3-ClC6H4
4-MeOC6H4
4-NO2C6H4
3-NO2C6H4
1-Naphth
C6H5
C6H5
C6H5
C6H5
4-MeC6H4
C6H5
30
30
10
30
30
30
30
10
30
30
30
30
30
60
60
30
4f
4g
4h
4i
4j
4k
4l
4m
4n
4o
4p
4q
4r
4s
4t
4u
4v
4w
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
4-MeC6H4
4-EtC6H4
4-ClC6H4
4-BrC6H4
4-ClC6H4
C6H5
4-MeOC6H4
4-MeOC6H4
4-MeOC6H4
4-MeOC6H4
4-MeOC6H4
C6H5
4-MeC6H4
C6H5
C6H5
4-MeC6H4
30
30
30
30
30
30
C6H5
4-ClC6H4
C6H5
C6H5
C6H5
c
-Pr
n
-C5H11
a
All the reactions were performed with
1 (1.0 mmol), 2 (1.2 mmol), 3 (2.0 mmol), Cu(OTf)2 (36 mg, 0.1 mmol), L1 (36 mg, 0.1 mmol), silica gel
(chromatography grade, 0.8 g), and stainless-steel balls (1.5 cm*2) in a stainless-steel jar under ball-milling at 25 Hz. b Isolated yields based on . c %ee
1
were determined by HPLC after chromatography separation. d The absolute configuration was assigned by analogy according to the reported HPLC retention
times.
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%yield
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Acknowledgements
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2
3
4
5
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Figure 1. Recyclibility chart (recyclability of the catalytic system was tested on the
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This journal is © The Royal Society of Chemistry 2015
Green Chem., 2015, 00, 1-4 | 3

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Green Chemistry
View Article Online
DOI: 10.1039/C5GC00079C
Chiral propargylamines were prepared by a ball-milling promoted, fast, high yielding, highly enantioselective
solvent-free A3 reaction using a recoverable catalyst.