Supporting Information

A Recyclable Catalytic Dendrimer Nanoreactor for Part-

Per-Million CuI Catalysis of “Click” Chemistry in Water
Christophe Deraedt, Noel Pinaud, Didier Astruc*

ISM, Univ. Bordeaux, 351 Cours de la Libération, 33405 Talence Cedex, France. E-mail:
[email protected]

I. General data……………………………………………S2

II. Syntheses of catalyst 2 and catalyst 1-CuI.......................S3

III. Encapsulation of the catalyst 2 in dendrimer 1……......S4

IV. Complexation of CuI to the triazoles of dendrimer 1…S9

V. CuAAC (procedure and 1H NMR of final products)….S13

VI. Synthesis and characterization of 3, 4, 5...…………....S31

VII. Kinetic study of the auto-catalysis……………………S36

VIII. Dendrimer 1 as a recyclable catalyst…………………..S37

S1
I. General data
All the solvents (THF, CH2Cl2, Et2O) and chemicals were used as received. 1,4-
dioxane and CH3CN were distilled on sodium.
1
H NMR, 13C NMR, DOSY NMR and NOESY NMR spectra were recorded at 25°C
with a Bruker AC 200, 300, 400 or 600 (200, 300, 400 or 600 MHz) spectrometer.
All the chemical shifts are reported in parts per million (δ, ppm) with reference to
Me4Si (TMS) for the 1H NMR spectra. The mass spectra were recorded at the
CESAMO (Univ. Bordeaux) with a QStar Elite mass spectrometer (Applied
Biosystems). The instrument is equipped with an ESI source, and spectra were
recorded in the positive mode. The electropray needle was maintained at 5000 V and
operated at room temperature. Samples were introduced by injection through a 20 µL
sample loop into a 4500 µL min–1 flow of methanol from the LC pump.

S2
II. Syntheses of catalyst 2 and catalyst 1-CuI

Synthesis of the catalyst 1-CuI: In a Schlenk flask, 3.59 x 10-7 mol of G0-27 TEG 1
(2.59 mg) solubilized in 1 mL of degassed water and 9 equiv. CuSO4.5H2O (3.10 x
10-6 mol, i.e. 0.8 mg) solubilized in 1 mL of water are successively added. 12 mL of
degassed water are added in the Schlenk flask, and the solution is stirred at r.t. in 20
min under N2. 1.55 x 10-5 mol of sodium ascorbate (3.06 mg) solubilized in 1 mL of
degassed water is added dropwise to the solution of 1-CuII. After stirring 15 min
under N2, the air-sensitive solution is ready for use. In situ reduction of CuII to CuI
with excess NaAsc (10 equiv. per Cu) is recommended in the case of CuAAC
reactions that are conducted with a very small (down to 1 ppm) amount of catalyst.

Improved synthesis of the ligand hexa(benzyl)tren of catalyst 2: A suspension of dry

benzylbromide (1.5 g, 8.8 mmol), tris(2-aminoethyl)amine (0.18 g, 1.3 mmol) and dry
K2CO3 (1.9 g, 13.8 mmol) is heated under refluxed conditions in distilled CH3CN
under N2. After 48 h, the solvent is evaporated, and 50 mL of CH2Cl2 are added. The
solution is washed with H2O (3 x 50 mL), the organic phase is dried over Na2SO4, the
solvent is removed in vacuo, and the resulting solid is washed several times with
methanol giving hexa(benzyl)tren as a light-yellow gel; yield: 0.84 g (97.7%). 1H
NMR (CDCl3, 200 MHz): d = 7.42 (30 H, CH, arom.), 3.6 (12H, NCH2Cq), 2.55,
(12H, NCH2CH2N); 13C NMR (CDCl3, 75 MHz): d = 138.7 (NCH2Cq), 127.7, 127.0,
125.7 (CH arom.), 57.7 (NCH2Cq), 51.9 (NCH2CH2N*), 50.3 (NCH2CH2N*); anal.
calcd. for C48H54N4: C 83.92, H 7.92; found: C 83.64, H 7.96; MS (MALDI-TOF):
m/z = 687.5, calcd. for C48H54N4: 686.2.35

S3
III. Encapsulation of catalyst 2 in dendrimer 1
1°) 1H NMR spectra.
G0-27 TEG dendrimer 1 1H NMR spectrum in D2O.

Figure S1: 1H NMR spectrum of 1 in D2O.

1
H NMR (D2O, 600 MHz) δppm: 7.87 (CH-triazole), 6.88 (CH-arom. intern), 6.61
(CH- arom. extern), 4.57 (triazole-CH2-0), 4.40 (O-CH2-arom. extern), 4.04-4.09
(CH2O-arom. extern), 3.90 (Si-CH2-triazole), 3.51-3.78 (OCH2CH2O), 3.29-3.32
(CH3O), 1.49 (CH2CH2CH2Si), 0.97 (CH2CH2CH2Si), 0.474 (CH2CH2CH2Si), -0.076
(Si(CH3)2).

S4
Figure S2: Comparison between the 1H NMR spectrum of catalyst 2 + 1 and that of 1
in D2O (zone affected by a shift of proton). A: 3.294-4.567 ppm, B: -0.076-1.486
ppm.

S5
1
H NMR proton 1 proton 2 proton 3 proton 4 proton 5 proton 6
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
1 -0.076 0.474 0.972 1.486 3.33 7.874
1+2 -0.065 0.478 0.985 1.498 3.29 7.958
1
H NMR proton 7 proton 8 proton 9 proton 10 proton 11 proton 11
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
1 6.886 6.615 4.567 4.404 4.090 4.046
1+2 6.875 6.588 4.594 4.380 4.086 4.028
1
H NMR proton 12 proton 13
(ppm) (ppm)
1 3.901 -0.076
1+2 3.933 -0.065
1
Table 1. H NMR shifts of all the protons (see Figure 1 for the numbers that are
assigned to the protons) of 1 alone and 1+2. Red values correspond to protons that are
shifted by > 0.02 ppm.

Figure S3: 1H NMR spectra of 1 + 2 in D2O at three different concentrations. A: [1] =

2.8 x 10-3 M, 1 equiv. catalyst 2 is observed for 15 equiv. dendrimer 1. B: [1] = 9.3 x
10-4 M, 1 equiv. catalyst 2 is observed for 7 equiv. dendrimer 1. C: [1] = 3.2 x 10-4 M,
1 equiv. catalyst 2 is observed for 5 equiv. dendrimer 1.

S6
2°) Interpretation of the DOSY NMR spectra
Determination of the dendrimer radius in solution using the diffusion coefficient
determined by 1H NMR:
A 1H NMR experiment focuses on the diffusion that is mathematically treated
according to a DOSY process (Diffusion Ordered Spectroscopy) in order to obtain the
equivalent of a spectral chromatography. The objective is to measure the diffusion
coefficient D of the molecules in solution that gives access to the hydrodynamic
radius.
The dendrimers are considered as spherical molecular objects, and they are
characterized by an apparent diffusion coefficient. The application of the Stokes-
Einstein law gives an estimate of the hydrodynamic radius of the molecule.
Stokes-Einstein law: D = KBT / 6лηrH

D: diffusion constant; KB: Boltzman’s constant; T: temperature (K); η: solvent

viscosity; rH: hydrodynamic radius of the species.

DOSY: D = 2.9 (± 0.1) x 10-11m2/s (concentrated [1] = 2.8 x 10-3 M)

KB = 1.38 x 10-23 m2.kg.s-2.K-1
T = 298 K
η = 1.132 x 10-3 Pa.s

→ rH = KBT/6лηD = 6.6 (±0.1) nm

→ Hydrodynamic diameter of 1: 13.3 (± 0.2) nm

D = 3.8 (± 0.1) x 10-11m2/s (diluted [1] = 8.7 x 10-5 M)

KB = 1.38 x 10-23 m2.kg.s-2.K-1
T = 298 K
η = 1.132 x 10-3 Pa.s

→ rH = KBT/6лηD = 5.1 (±0.1) nm

→ Hydrodynamic diameter of 1: 10.2 (± 0.2) nm

S7
3°) NOESY NMR spectrum.

Figure S4: NOESY 1H NMR spectrum of 1 + 2 in D2O with [1]: 2.8 x 10-3 M. A
correlation between the two peaks of 2 and the six protons of Si(CH3)2 of 1 is
observed.

S8
IV. Complexation of CuI to the triazoles of the dendrimer 1

Figure S5: 1H NMR spectrum (400 MHz) of dendrimer 1 in D2O before copper
complexation.

S9
Figure S6: 1H NMR spectrum (400 MHz) of dendrimer 1 + CuSO4.5H2O in D2O. The
triazole signal of 1 becomes broader.

S10
 Figure S7: 1H NMR spectrum (400 MHz) of dendrimer 1 + CuSO4.5H2O + NaAsc
(NaAsc was added directly to the precedent D2O solution containing dendrimer 1 +
CuSO4.5H2O) in D2O. The triazole signal of 1 reappears at 8.08 ppm, revealing the
presence of diamagnetic copper species (CuI).

S11
Figure S8: superposition of the three previous 1H NMR spectra (400 MHz).

S12
V. CuAAC (procedure and 1H NMR of final products)

General procedure for the CuAAC reaction with catalyst 2: A Schlenk flask is
charged with 0.105 mmol of alkyne, 0.1 mmol of organic azide and 0.1% mol of
catalyst 2 (0.075 mg). 1% mol of dendrimer 1 (7.2 mg) is dissolved in 2 mL of water,
then added into the Schlenk tube. The reaction is stirred during 3 hours at 25°C under
N2. The final product is extracted from water with CH2Cl2 (3 x 5 mL). The organic
layer is dried with Na2SO4 and the solvent is removed in vacuo to give the
corresponding 1,2,3-triazole. The product is then purified by silica chromatography.
Another purification consists in extracting the product from water with Et2O (3 x 5
mL), drying with Na2SO4 removing the solvent in vacuo to give the corresponding
1,2,3-triazole. The advantage is that 1 remains in the aqueous solution and is
completely recovered. The product is then also purified by silica chromatography
when necessary.

General procedure for the CuAAC reaction with 1-CuI: A glass vessel is charged
with 1.05 mmol of alkyne and 1 mmol of organic azide. The solution of 1-CuI is
added into the vessel (1-0.0001 mol % of CuI) under N2, and degassed water is added
in order to obtain 1 mL as total volume of water. The reaction is stirred during 24h at
30°C under N2. Excess of NaAsc (up to 0.1 mol %) can be added in the vessel in
order to overcome the problem of air sensitivity. The final product is extracted from
water with CH2Cl2 (3 x 10 mL). The organic layer is dried with Na2SO4 and the
solvent is removed in vacuo to give the corresponding 1,2,3-triazole. The product is
then purified by silica chromatography when necessary.

S13
1-benzyl-4-phenyl-1H-[1,2,3]triazole was isolated as a white solid.

Figure S9: 1H NMR spectrum of 1-benzyl-4-phenyl-1H-[1,2,3]triazole.

1
H NMR (300 MHz, CDCl3) δppm: 7.83-7.86 (m, 2H), 7.73 (s, 1H), 7.34-7.46 (m,
5H), 5.57 (s, 2H).

No trace of the isomer 1-benzyl-5-phenyl-1H-[1,2,3]triazole is observed on TLC.

Moreover, the 1H NMR spectrum is clearly different (see below). Thus there is no
doubt: only the CuAAC reaction occurs (the uncatalyzed Huisgen reaction giving two
isomers does not occur).

S14
Figure S10: 1H NMR spectrum of 1-benzyl-5-phenyl-1H-[1,2,3]triazole.

S15
1-benzyl-4-(trimethylsilyl)-1H-[1,2,3]triazole was isolated as a yellow liquid.

Figure S11: 1H NMR spectrum of 1-benzyl-(trimethylsilyl)-1H-[1,2,3]triazole.

1
H NMR (300 MHz, CDCl3) δppm: 7.40 (s, 1H), 7.32-.33 (m, 3H), 7.25 (d, 2H), 5.52
(s, 2H), 0.26 (s, 9H).

S16
4-(1-benzyl-1H-[1,2,3]triazol-4-yl)-benzaldehyde was isolated as a white solid.

Figure S12: 1H NMR spectrum of 4-(1-benzyl-1H-[1,2,3]triazol-4-yl)-benzaldehyde.

1
H NMR (300 MHz, CDCl3) δppm: 9.97 (s, 1H), 7.86-7.96 (m, 4H), 7.76 (s, 1H),
7.28-7.38 (m, 5H), 5.57 (s, 2H).

S17
(1-Benzyl-1H-1,2,3-triazol-4-yl)methanol

Figure S13: 1H NMR spectrum of (1-benzyl-1H-1,2,3-triazol-4-yl)methanol.

1
H NMR (300 MHz, CDCl3) δppm: 7.42 (s, 1H), 7.33-7.35 (m, 3H), 7.24-7.25 (m,
2H), 5.479 (s, 2H), 4.726 (s, 2H).

S18
1-[(3-methylphenyl)methyl]-4-phenyl-1H-[1,2,3]triazole: was isolated as a white
solid.

Figure S14: 1H NMR spectrum of 1-[(3-methylphenyl)methyl]-4-phenyl-1H-

[1,2,3]triazole.
1
H NMR (300 MHz, CDCl3) δppm: 7.79-7.84 (m, 2H), 7.669 (s, 1H), 7.26-7.46 (m,
4H), 7.10-7.20 (m, 3H), 5.55 (s, 2H), 2.36 (s, 2H).

S19
3-(1-Benzyl-1H-[1,2,3]triazol-4-yl)-pyridine: was isolated as a yellowish solid.

Figure S15: 1H NMR spectrum of 3-(1-benzyl-1H-[1,2,3]triazol-4-yl)-pyridine.

1
H NMR (300 MHz, CDCl3) δppm: 8.97 (s, 1H), 8.55-8.56 (d, 1H), 8.15-8.19 (m, 1H),
7.80 (s, 1H), 7.30-7.42 (m, 6H), 5.60 (s, 2H).

S20
1-benzyl-4-(4-bromophenyl)-1H-[1,2,3]triazole was isolated as a white solid.

Figure S16: 1H NMR spectrum of 1-benzyl-4-(4-bromophenyl)-1H-[1,2,3]triazole.

1
H NMR (300 MHz, CDCl3) δppm: 7.66-7.70 (m, 3H), 7.50-7.55 (m, 2H), 7.27-7.41
(m, 5H), 5.82 (s, 2H).

S21
1-(4-bromo-benzyl)-4-phenyl-1H-[1,2,3]triazole was isolated as a white solid.

Figure S17: 1H NMR spectrum of 1-(4-bromo-benzyl)-4-phenyl-1H-[1,2,3]triazole.

1
H NMR (300 MHz, CDCl3) δppm: 7.76-7.80 (m, 2H), 7.65 (s, 1H), 7.47-7.52 (m,
2H), 7.30-7.43 (m, 3H), 7.14-7.18 (d, 2H), 5.51 (s, 2H).

S22
4-(4-phenyl-[1,2,3]triazol-1-ylmethyl)-benzonitrile was isolated as a white solid.

Figure S18: 1H NMR spectrum of 4-(4-phenyl-[1,2,3]triazol-1-ylmethyl)-benzonitrile.

1
H NMR (300 MHz, CDCl3) δppm: 7.80-7.84 (m, 2H), 7.74 (s, 1H), 7.66-7.70 (m,
2H), 7.37-7.43 (m, 5H), 5.65 (s, 2H).

S23
1,4-diphenyl-1H-[1,2,3]triazole was isolated as a light brown solid.

Figure S19: 1H NMR spectrum of 1,4-diphenyl-1H-[1,2,3]triazole.

1
H NMR (300 MHz, CDCl3) δppm: 8.21 (s, 1H), 7.91-7.96 (m, 2H), 7.79-7.83 (m,
2H), 7.55-7.60 (m, 2H), 7.42-7.48 (m, 3H), 7.34-7.38 (m, 1H).

S24
(1-benzyl-1H-[1,2,3]triazol-4-yl)-diphenylmethanol was isolated as a white solid.

Figure S20: 1H NMR spectrum of (1-benzyl-1H-[1,2,3]triazol-4-yl)-

diphenylmethanol.
1
H NMR (300 MHz, CDCl3) δppm 7.37-7.46 (m, 16H), 5.57 (s, 2H), 3.84 (s, 1H).

S25
(1-benzyl-1H-[1,2,3]triazol-4-yl)-methanoic acid was isolated as a white solid.

Figure S21: 1H NMR spectrum of (1-benzyl-1H-[1,2,3]triazol-4-yl)-metanoic acid.

1
H NMR (200 MHz, DMSO) δppm: 7.89 (s, 1H), 7.34-7.29 (m, 5H), 5.51 (s, 2H),
4.85 (s, 1H).

S26
(1-benzyl-1H-[1,2,3]triazol-4-yl)-coumarin was isolated as a white solid.

Figure S22: 1H NMR spectrum of (1-benzyl-1H-[1,2,3]triazol-4-yl)-coumarin.

1
H NMR (200 MHz, DMSO) δppm: 8.46 (s, 1H), 7.98-7.94 (d, 1H), 7.63-7.59 (d,
1H), 7.34 (m, 5H), 7.10 (s, 1H), 7.00-6.96 (d, 1H), 6.30-6.25 (d, 1H), 5.64 (s, 2H),
5.31 (s, 2H), 4.90 (s, 1H).

S27
(1-benzyl-1H-[1,2,3]triazol-4-yl)-cyclohexylmethanol was isolated as a white solid.

Figure S23: 1H NMR spectrum of (1-benzyl-1H-[1,2,3]triazol-4-yl)-

cyclohexylmethanol.
1
H NMR (200 MHz, CHCl3) δppm: 7.37-7.21 (m, 6H), 5.47 (s, 2H), 2.78 (s, 1H),
1.94-1.28 (m, 10H).

S28
(1-benzyl-1H-[1,2,3]triazol-4-yl)-propane was isolated as a colorless liquid.

Figure S24: 1H NMR spectrum of (1-benzyl-1H-[1,2,3]triazol-4-yl)-propane.

1
H NMR (200 MHz, CHCl3) δppm: 7.40-7.20 (m, 6H), 5.50 (s, 2H), 2.70-2.63 (t, 2H),
1.73-1.62 (q, 2H), 0.98-0.91 (t, 3H).

S29
(1-octyl-1H-[1,2,3]triazol-4-yl)-phenyl was isolated as a colorless liquid.

Figure S25: 1H NMR spectrum of (1-octyl-1H-[1,2,3]triazol-4-yl)-phenyl.

1
H NMR (200 MHz, CHCl3) δppm: 7.86-7.80 (d, 2H), 7.75 (s, 1H), 7.46-7.27 (m,
3H), 4.44-4.39 (t, 2H), 1.97-1.90 (t, 2H), 1.38-1.27 (m, 10H), 0.90-0.85 (t, 3H).

S30
VI. Synthesis and characterization of 3, 4, and 5
- Dendrimer G1-81 TEG, 3

Scheme S1: synthesis of dendrimer 3

3 has been synthesized following the reference 39 of the main text.
27-azido core (0.073 g, 0.012 mmol) and the alkyne tris TEG dendron (0.199 g, 0.388
mmol, 1.2 equiv. per branch) are dissolved in THF. CuSO4.5H2O is added (0.079 g,
0.323 mmol, 1 equiv. per branch, 1M in aqueous solution), followed by the dropwise
addition of a freshly prepared solution of sodium ascorbate (0.125 g, 0.646 mmol, 2
equiv. per branch, 1M in water solution) in order to set a 1:1 THF/water ratio. The
reaction mixture is stirred for 3 days at 25°C under N2. After removing THF in vacuo,
CH2Cl2 (100 mL) and an aqueous ammonia solution (2.0 M, 50 mL) are successively
added. The mixture is allowed to stir for 10 minutes in order to remove all the CuII
trapped inside the dendrimer as [Cu(NH3)2(H2O)2] [SO4]. The organic phase is
washed twice with water, then this operation is repeated three more times to ensure
the complete removal of copper ions. The organic phase is dried with sodium sulfate,
and the solvent is removed in vacuo. The product is washed with 50 mL diethyl ether
several times in order to remove the excess of the dendron. 0.180 g of 3 is obtained
(68 % yield).

S31
- Monomer 4

Scheme S2: synthesis of monomer 4

Benzyl azide (0.050 g, 0.376 mmol) and the alkyne dendron (0.237 g, 0.376 mmol, 1
equiv.) were dissolved in THF, CuSO4. 5H2O was added (0.047 g, 0.188 mmol, 0.5
equiv. in 1.5 mL of water), followed by dropwise addition of a freshly prepared
solution of sodium ascorbate (0074 g, 0.376 mmol, 1 equiv. in 1.5 mL of water) in
order to set a 1:1 THF/water ratio. The reaction mixture was stirred overnight at 25°C
under N2. After removing THF in vacuo, CH2Cl2 (20 mL), an aqueous ammonia
solution (2.0 M, 20 mL) was added. The mixture was allowed to stir for 2 minutes in
order to remove all the copper as [Cu(NH3)2(H2O)2] [SO4]. The organic phase was
washed twice with water, dried with sodium sulfate, and the solvent was removed in
vacuo. The product was washed with pentane and Et2O, and 260 mg of the desired
product 4 was obtained (90% of yield). 4 has been characterized by 1H NMR, 13C
NMR and ESI mass analysis.

Figure S26: mass spectrum of 4.

The theoretical mass is 765 g. mol-1, and a peak at 788 g.mol-1 is observed (765 + Na),
which confirms the presence of the desired product.

S32
Figure S27: 1H NMR spectrum of 4.
1
H NMR (300 MHz, CDCl3) δppm: 7.5 (s, 1H, trz), 7.28-7.39 (m, 5H, benzyl), 6.58
(s, 2H, aromatic of the dendron), 5.54 (s, 2H, benzyl-CH2-trz), 4.64 (s, 2H, trz-CH2-
O), 4.48 (s, 2H, O-CH2-aromatic of the dendron), 4.11-4.18 (m, 6H, aromatic of the
dendron-O-CH2-), 3.54-3.85 (m, 30H, O-CH2-CH2-O), 3.38 (s, 9H, O-CH3).

S33
Figure S28: 13C NMR spectrum of 4.
13
C NMR (100 MHz, CDCl3) δppm: 152 (Cq aromatic dendron), 145.8 (Cq trz), 138.2
(Cq-CH2-O), 134 (Cq-CH2-O), 133-128 (CH-benzyl), 122 (CH trz), 107 (CH
aromatic dendron), 72-69 (OCH2CH2O), 63.3 (triazole-CH2-O), 59 (CH3O), 54.4
(aromatic-CH2-trz).

- Dendrimer 5 (that does not contain triazole rings)

Scheme S3: synthesis of dendrimer 5

5 has been synthesized following reference 40 of the main text.
The 9-iodo core (5.46 x 10-6 mol) and the phenol dendron (10 equiv.) were
introduced into a Schlenk flask, and dry DMF (30 mL) was added, then K2CO3 (2
equiv per dendron) was added to the solution. The mixture was stirred for 2 days at
80 °C under reflux. At the end of the reaction, DMF was removed in vacuo. The
product was extracted with CH2Cl2 and washed with water. 5 was purified by

S34
chromatography (CH2Cl2:MeOH, (97:3) to remove the excess dendron and then
(90:10) to extract the dendrimer. Isolated yield = 80%

Complexation of copper to the triazole derivative 4.

In a Schlenk flask, 3.1 x 10-6 mol of 4 (2.37 mg) solubilized in 1 mL of degassed

water and 1 equivalent of CuSO4.5H2O (3.10 x 10-6 mol i.e. 0.8 mg) solubilized in 1
mL of water were successively added. 12 mL of degassed water was added in the
Schlenk, and the solution was stirred at r.t. during 20 minutes under N2. 1.55 x 10-5
mol of sodium ascorbate (3.06 mg) solubilized in 1 mL of degassed water was added
dropwise to the solution of 1-CuII. After 15 minutes of stirring under N2, the solution
was ready for use.

S35
VII. Kinetic study of the auto-catalysis
The reaction was performed with 10 mg of nona-azido core, 55 mg of tris TEGylated
alkynyl dendron (1.5 equiv. per branch), 8% mol of 2 per branch, and with or without
5 mg of 1 (1% mol per branch) in 1.5 mL of D2O at 30°C.

Figure S29. 1H NMR spectra of the auto-catalysis after 90, 210, 330, 450, 570, and
690 min. The decrease in intensity of the signal of the aromatic protons of the starting
material and the increase in intensity of the signal of the aromatic protons of the final
product allow to determine the conversion of the reaction.

Figure S30. Kinetic studies of the reaction with (left) and without (right) 1 at the
beginning of the reaction. After 570 min, the reaction is finished when 1 is present at
the beginning of the reaction, whereas only 20% of conversion is reached without 1.

S36
VIII. Dendrimer 1 as a recyclable catalyst

General procedure for the recovery of 1: after the CuAAC reaction, the desired
product is extracted from water twice with 5 mL of Et2O. The water phase contains 1
that is not soluble in Et2O, and in the case of the reuse of 1, the water phase is directly
used for the next reaction (after complete evaporation of the traces of Et2O).
Alternatively, in the case of the recovery of 1, after extraction of the desired product
from water with Et2O, the resulting water phase is extracted twice with 5 mL of
CH2Cl2. The CH2Cl2 phases are gathered, dried with Na2SO4, and the solvent is
removed in vacuo in order to quantitatively recover 1 (see the 1H NMR aand IR
spectra of 1 after 10 uses in the Supporting Information, Figures S31 and S32).
Moreover, most of the “click” compounds presented here are water insoluble solids,
thus a simple filtration allows obtaining the desired product and retaining the water
solution of the dendrimer.

S37
Figure S31: 1H NMR spectrum (300MHz in CDCl3) of 1 after 10 uses. No change is
observed (no shift, and the integrations are correct) by comparison with the 1H NMR
spectrum of the starting dendrimer.

Figure S32: IR spectrum of 1 after 10 uses. No change is observed by comparison

with the IR spectrum of the starting dendrimer 1.

S38