Click approaches to functional water-sensitive organotriethoxysilanes

Article abstract of DOI:10.1021/jo201484n

The derivatization of functional organic fragments with triethoxysilyl groups to afford hydrolyzable organosilanes with targeted properties using the copper-catalyzed alkyne azide cycloaddition reaction under strictly anhydrous conditions is described acc

Full text of DOI:10.1021/jo201484n

FEATURED ARTICLE
pubs.acs.org/joc
Click Approaches to Functional Water-Sensitive
Organotriethoxysilanes
Kristꢀyna B€urglovꢀa,†,‡ Nirmalya Moitra,† Jana Hodaꢁcovꢀa,‡ Xavier Catto€en,†,* and Michel Wong Chi Man†,*
†
0ꢀ
Institut Charles Gerhardt Montpellier (UMR 5253 CNRS-UM2-ENSCM-UM1), 8, rue de l Ecole Normale, 34296 Montpellier,
France
‡Department of Organic Chemistry, Institute of Chemical Technology, Technickꢀa 5, 16628 Praha 6, Czech Republic.
S Supporting Information
b
ABSTRACT: The derivatization of functional organic fragments with
triethoxysilyl groups to afford hydrolyzable organosilanes with targeted
properties using the copper-catalyzed alkyne azide cycloaddition reaction
under strictly anhydrous conditions is described according to two ap-
proaches, starting from five silylated substrates. This high yield, fast, and
selective method is applicable to a wide range of substrates and is expected
to lead to important achievements in the field of functional hybrid silica.
Scheme 1. Two Retrosynthetic Approaches to Organo-
trialkoxysilanes Using the Click Reaction
’ INTRODUCTION
Functional organosilicas are promising materials for applica-
tions in diverse fields such as optics,1ꢀ3 coatings,4 separation,5
drug delivery,6 or supported catalysis.7ꢀ9 Organotrialkoxysilanes
are key intermediates for the synthesis of such hybrid materials.
These can be formed either directly from molecular precursors
using the solꢀgel process or by postfunctionalizing a preformed
material (grafting). Since organotrialkoxysilanes are moisture
sensitive, it is preferable to functionalize the organic fragment
with a trialkoxysilyl group in the late steps of the synthesis. For
this reason, it is desirable to use reactions affording the com-
pounds with easy purification steps that can be performed under
anhydrous conditions and avoid any chromatographic separa-
tion. Therefore, elaborated functional organotriethoxysilanes are
often prepared by hydrosilylation or rhodium-catalyzed silylation
of aromatic halides using triethoxysilane, by formation of tertiary
amines from 3-aminopropyltriethoxysilane (APTES) or 3-chlor-
opropyltriethoxysilane (ClPTES), or by formation of urea and
carbamate linkers using 3-isocyanatopropyltriethoxysilane
(ICPTES). Alternatively, the addition of organometallic reagents
to tetrachlorosilane followed by alcoholysis has already been
described, but it usually leads to complicated mixtures from
which the compound can only be extracted by distillation or by
crystallization. Despite the variety of the already existing syn-
thetic methods and reagents, some substrates are still challen-
ging, as the triethoxysilyl moiety is incompatible with various
chemical functions (such as alcohols10 and acids11), as some 1,6-
diene groups usually yield cyclic byproducts using radical or
organometallic chemistry, and as the use of hydrosilanes can also
lead to a partial reduction of the double bonds. The rapid
development of the copper-catalyzed alkyne azide cycloaddition
reaction (CuAAC) in bio-organic, polymer, and materials
Scheme 2. Silylated Substrates Containing Functionalities
That Can Undergo Click Reactions
chemistry12 prompted us to envisage its use to link an organic
function bearing a triple bond with an alkyltriethoxysilane moiety
using this click reaction.13 Applying microwave activation, a very
fast and selective method was developed that yields organo-
triethoxysilanes in high yield and purity with only simple
Received: July 18, 2011
Published: August 17, 2011
r
2011 American Chemical Society
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Table 1. Reaction of AzPTES 1 with Functional Alkynesa
Scheme 3
Scheme 4
Table 2. Evaluation of the Alkyne-Based Precursors for the
Click Reactiona
substrate
catalyst loading (%)
conversion (%)
1
2
3
4
5
6
2
3
3
3
4
5
0.5
0.5
2
60
0
50
2.5
0.5
0.5
100
100
100
a Alkyne (2 mmol), azide (2 mmol), CuBr(PPh3)3, THF/Et3N 1:1
(1 mL), microwave, 100 °C, 5 min.
approach (B). In particular, we will focus on triethoxysilyl substrates
(Scheme 2) containing functionalities (azide or terminal alkyne)
that can undergo click reactions to give new organosilanes, pre-
cursors of hybrid silicas that can be used for several interesting
applications such as optics, biomaterials, and catalysis.
’ RESULTS AND DISCUSSION
Considering the first retrosynthesis, which implies the reaction of
3-azidopropyltriethoxysilane 1 (AzPTES)15,16 with organic alkynes,
our preliminary report13 described an efficient transformation that
can be carried out in 5 min under microwave conditions. This
method was proven to be compatible with several functionalities,
such as amine (from primary to tertiary), N-heterocycle, alcohol,
diol, ether, and ester. As seen in Table 1, the scope can be extended
to other functional groups showing the versatility of the method. In
all cases, full conversion was obtained (as determined by 1H NMR).
Indeed, a thioether derivative that is known to poison catalysts can be
incorporated, although slightly more catalyst amount and reaction
time was necessary (entry 1). The epoxide functionality can also be
preserved thanks to the anhydrous conditions (entry 2).17 The
obtained phenylglycidol ether may subsequently be functionalized to
afford chiral catalysts such as bis(oxazolines),18,19 phosphinite
a Reaction conditions: alkyne (2 mmol), azide (2 mmol), CuBr-
(PPh3)3 (0.01 mmol), THF/Et3N 1:1 (1 mL), microwave, 100 °C,
5 min. b 0.02 mmol of CuBr(PPh3)3, reaction time: 10 min. c 0,05 mmol
of CuBr(PPh3)3, reaction time: 1 h. d DMF was used instead of THF,
reaction time: 10 min. e Reaction time: 10 min.
extraction and filtration workup procedures. With this method, the
triethoxysilyl groups could be incorporated into challenging sub-
strates, allowing the formation of new types of organotriethoxysi-
lanes. A similar synthesis was very recently used for preparing
solꢀgel precursors bearing fluorescent functional groups.14 In this
paper, we will describe the scope of this first method (retrosynthesis
(A), Scheme 1), and develop the complementary retrosynthetic
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Table 3. Reaction of 4 with azides a
a Reaction conditions: alkyne (2 mmol), azide (2 mmol), CuBr(PPh3)3 (0.01 mmol), THF/Et3N 1: 1 (1 mL), microwave, 100 °C, 5 min. b Reaction
time: 10 min
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Table 4. Reaction of 5 with Azidesa
thioethers,20 or β-amino alcohols.21 Notably, the click alkyl-
silylation can be performed on a preformed amino alcohol
derivative19 (entry 3). Imidazolium salts are also very im-
portant in catalysis, as they can form NHC complexes or act as
organocatalysts. Therefore, we first performed this click
functionalization on propargyl(methyl)imidazolium iodide.
However, under the standard reaction conditions, a 1:1
mixture of the expected organosilane and allene resulting
from the isomerization of the propargyl group, was observed
(Scheme 3). To circumvent this issue, a pent-4-ynyl group
was used (entry 4). Although the reaction was slow, full
conversion could be attained. However, because of the high
loading of catalyst used, the product was contaminated with
triphenylphosphine oxide (ca. 15%).13 We then focused our
efforts on the synthesis of silylated dyes that are useful for a
wide range of applications (in sensing, labeling...).22 Pyrene
and aminonaphthalimide23 derivatives could be easily func-
tionalized (entries 5 and 6). Because of the low solubility of
the starting compound, the latter reaction was performed with
full conversion in anhydrous DMF, without any important
change in the reaction conditions. Furthermore, the electro-
active ferrocene derivative could be selectively functionalized
(entry 7). This silylation method also allows an alternative
approach to adenine-based solꢀgel precursors (entry 8) for
the synthesis of bio-inspired materials.24
Following this first retrosynthetic approach, we considered
further developing the click approach to solꢀgel precursors with
the triethoxysilyl group linked to the terminal triple bond.
Indeed, it is sometimes easier to incorporate an azide group
rather than an alkyne function on a functional organic fragment.
The design and preparation of four silylated terminal alkynes
were thus proposed through various linkers (Schemes 2 and 4).
Thioether derivatives 2 (Scheme 2) and 3 were obtained by
alkylation of 3-triethoxysilylpropylthiolate with propargyl
bromide25 or 5-iodopent-1-yne, respectively (Scheme 4).
The previously reported silylated substrate with a ureido
linker, 4 (Scheme 2), was also used.26 Moreover, (3-di(prop-
2-yn-1-yl)aminopropyl)triethoxysilane 5 with two alkynyl
functions located in close proximity was synthesized by
reaction of APTES with propargyl bromide in the presence
of a base. These four precursors were then evaluated as
potential candidates for the click-alkylsilylation reaction with
benzyl azide under the standard conditions (Table 2). With 2,
the conversion observed was only 60% (entry 1), probably due
to a deactivation of the catalyst by the thioether function (as
seen in Table 1 entry 1). Furthermore, besides the expected
coupling product, the isomerized allene (ca. 10%) was also
observed (Scheme 3). A blank reaction performed with
neither catalyst nor azide evidenced the partial formation of
the allene with 11% conversion. To prevent this side reaction,
a longer chain was used: a 2.5% catalyst loading was necessary
to fully convert compound 3 under the same conditions
(entries 2ꢀ4). Much better results were achieved with com-
pounds 4 and 5 that lead to complete transformations under
the standard conditions (entries 5 and 6).
The urea functional group is capable of forming hydrogen
bonding, and therefore, its presence in the precursor molecule
can induce a nanostructuring of the material that is obtained
upon a solꢀgel hydrolysis/condensation process from organo-
trialkoxysilane precursors.27ꢀ29 For that reason, we studied the
use of 4 to produce organotrialkoxysilanes containing the urea
group. Reaction of 4 with different azides has been selected as
a Reaction conditions: alkyne (2 mmol), azide (2 mmol), CuBr(PPh3)3
(0.01 mmol), THF/Et3N 1:1 (1 mL), microwave, 100 °C, 5 min.
b Reaction time: 20 min.
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promising tool in this screening with the aim to produce
organotrialkoxysilanes possessing either one or more urea groups
or having both urea and the other functional group in the
molecule. The results are reported in Table 3.
pargyladenine,39 (2-azidoethyl) diethyl phosphonate,40 1-(azido-
methyl)pyrene41 9-(3-chloropropyl)adenine,42 hexyl azide,43 1,4-bis-
(azidomethyl)benzene,43 1,8-diazidodecane,43 and 1,3,5-tris(azido-
methyl)-2,4,6-trimethylbenzene44 were prepared according to published
procedures.
The production of monosilylated solꢀgel precursors was first
examined: the benzyl and hexyl adducts could be obtained in
excellent yields (Table 3, entries 1 and 2); functional groups such
as diethylphosphonate or hydroxyl are compatible with this
reaction (entries 3 and 4). In addition, pyrene and adenine
derivatives 7e and 7f could also be easily obtained (entries 5 and
6). These results demonstrate that both retrosynthetic ap-
proaches (Scheme 1) can be employed to produce these
important families of functional solꢀgel precursors (6e and 7e;
6h and 7f).22 Moreover, polysilylated precursors, which can yield
self-organized bridged silsesquioxanes by solꢀgel reactions,27ꢀ29
can also be formed. The dissymmetrical bridged organosilane 7g
was obtained by reaction of 1 with 4 (entry 7), whereas
symmetrical compounds can be synthesized from polyazides
(entries 8ꢀ10). Similarly, BINOL-derived bridged organosilanes
(MOM-protected or unprotected) were obtained (entries 11 and
12) with foreseen uses in supported asymmetric catalysis.30,31
As the H-bonding urea groups may interfere in the catalytic
or optical properties of the materials derived from 4, we
investigated the reactivity of 5, which lacks a self-assembling
group, in the click-alkylsilylation reaction (Table 4). As above,
the reactions proceed with full conversion and excellent yield
under the standard conditions despite the increased steric
hindrance (Table 4). In this case, the reaction with polyazides
would lead to mixed oligomers, precluding the production of
bridged systems.32
(3-(Pent-4-yn-1-ylthio)propyl)triethoxysilane (3). To a so-
lution of sodium hydride (95 wt %, 445 mg, 20.0 mmol) in dry THF
(100 mL) at ꢀ40 °C was added dry ethanol (920 mg, 20.0 mmol). After
20 min, 3-mercaptopropyltriethoxysilane (4.76 g, 20 mmol) was added.
The reaction mixture was brought to rt, stirred for 2 h, and was then
added dropwise to a solution of 5-iodopent-1-yne (3.86 g, 20.0 mmol) in
dry THF (50 mL). The mixture was left overnight at room temperature.
The solvent was distilled off and the residue extracted with dry pentane
(3 ꢁ 15 mL). Concentration of the pentane fractions yielded pure
compound 3 as a yellowish oil (5.29 g, 17.4 mmol). Yield: 87%. 1H NMR
(400 MHz, CDCl3) δ = 3.80 (q, J = 7.0 Hz, 6H), 2.60 (t, J = 7.2 Hz, 2H),
2.52 (t, J = 7.4 Hz, 2H), 2.30 (dt, J = 2.6 and 6.7 Hz, 2H), 1.95 (t, J = 2.6
Hz, 1H), 1.84ꢀ1.64 (m, 4H), 1.21 (t, J = 7.0 Hz, 9H), 0.76ꢀ0.69 (m,
2H). 13C NMR (100 MHz, CDCl3) δ = 83.6, 68.6, 58.4, 35.0, 30.7, 28.3,
18.3, 17.5, 9.9. HRMS (ESI+): calcd for C14H28O3SiSNa 327.1426,
found 327.1426.
(3-Di(prop-2-yn-1-yl)aminopropyl)triethoxysilane (5). To
a solution of 3-aminopropyltriethoxysilane (6.64 g, 30.0 mmol) in dry
THF (100 mL) were added calcium hydride (6.30 g, 150 mmol) and
propargyl bromide (80 wt % in toluene, 7.85 g, 66.0 mmol) successively.
The reaction mixture was stirred overnight at room temperature. After
evaporation of the solvents, extraction of the reaction mixture with
pentane and evaporation, compound 5 was obtained as a yellowish
viscous oil (8.57 g, 28.8 mmol). Yield: 96%. 1H NMR (400 MHz,
CDCl3) δ = 3.80 (q, J = 7.0 Hz, 6H), 3.43 (d, J = 2.5 Hz, 4H), 2.50 (t, J =
7.5 Hz, 2H), 2.20 (t, J = 2.5 Hz, 2H), 1.62ꢀ1.52 (m, 2H), 1.21 (t, J = 7.0
Hz, 9H), 0.65ꢀ0.58 (m, 2H). 13C NMR (100 MHz, CDCl3) δ = 77.8,
71.8, 57.3, 54.8, 41.0, 19.8, 17.3, 6.8. HRMS (ESI+): calcd for
C15H28NO3Si 298.1838, found 298.1831.
’ CONCLUSION
In conclusion, the CuAAC-alkylsilylation reaction appears
as an efficient, flexible, and wide-scope methodology for the
synthesis of organotrialkoxysilanes with targeted functional-
ities. In addition to our previous report,13 we have reported
here several new clickable alkyneꢀcontaining trialkoxysilanes
for the complementary retrosynthesis. These tools open new
perspectives in the field of functional organosilicas for a wide
range of applications. In addition, they may be extended to
the design of new functional silicone polymers. The set of
clickable trialkoxysilane solꢀgel precursors that is herein
described will also allow obtaining new functionalizable
organosilicas15,16,33 (e.g., as nanoparticles25 and thin films)
for the development of supported catalysts,34 sensors,22 and
nanomachines for drug delivery.35
General Procedure for the Click Reaction. A microwave tube
was filled under nitrogen with alkyne (2 mmol), azide (2 mmol/alkyne
function), [CuBr(PPh3)3] (0.01 mmol/alkyne function), dry triethyla-
mine (0.5 mL), and dry THF (0.5 mL) and then sealed. After 5 min
under microwave irradiation at 100 °C (maximum power =200 W), the
reaction mixture was allowed to cool, and then the solvents were
removed under vacuum. After addition of dry pentane, the mixture
was filtered, and then the filtrate was concentrated to afford the title
compound.
1
6a. Yield: 95%. H NMR (250 MHz, CDCl3) δ = 7.44ꢀ7.07 (m,
6H), 4.27 (t, J = 7.5 Hz 2H), 4.23 (s, 2H), 3.77 (q, J = 7.0 Hz, 6H),
2.02ꢀ1.88 (m, 2H), 1.20 (t, J = 7.0 Hz, 9H), 0.60ꢀ0.49 (m, 2H). 13C
NMR (100 MHz, CDCl3) δ = 144.7, 135.6, 129.5, 129.0, 126.4, 122.1,
58.5, 52.4, 28.9, 24.2, 18.3, 7.3. HRMS (ESI+): calcd for C18H30N3O3SSi
396.1777, found 396.1776.
1
6b. Yield: 95%. H NMR (400 MHz, CDCl3) δ = 7.57 (s, 1H),
’ EXPERIMENTAL SECTION
7.35ꢀ7.14 (m, 5H), 4.73ꢀ4.70 (m, 2H), 4.32 (t, J = 7.2 Hz, 2H), 3.89
(dd, J = 11.5 and 3.0 Hz, 1H), 3.79 (q, J = 7.0 Hz, 6H), 3.78ꢀ3.75 (m,
1H), 3.64 (dd, J = 11.5 and 5.4 Hz, 1H), 3.22ꢀ3.18 (m, 1H), 2.05ꢀ1.95
(m, 2H), 1.19 (t, J = 7.0 Hz, 9H), 0.61ꢀ0.55 (m, 2H). 13C NMR (100
MHz, CDCl3) δ = 144.5, 136.8, 128.5, 128.2, 125.7, 122.6, 70.1, 64.8,
60.9, 58.5, 55.8, 52.4, 24.2, 18.3, 7.5. HRMS (ESI+): calcd for
C21H34N3O5Si 436.2268, found 436.2252.
Caution. Azide compounds are potentially explosive. Great care and
protection are needed for heating of these compounds.
General Methods. All of the manipulations were carried out using
Schlenk techniques under a dry atmosphere of nitrogen. Microwave
reactions were carried out in sealed tubes using a microwave reactor
equipped with an infrared temperature sensor. NMR spectra were
recorded in dry CDCl3 at 298 K. 1H and 13C chemical shifts are reported
in ppm relative to Me4Si, and 31P chemical shifts are reported in
ppm relative to H3PO4. Organosilanes 1,15,16 2,25 4,26 phenylglycidol
propargyl ether,19 1-amino-1-phenyl-3-(prop-2-yn-1-yloxy)propan-2-
ol,19 (2S,4R)-dibenzyl 4-(prop-2-yn-1-yloxy)pyrrolidine-1,2-dicarboxy-
late,36 1-butyl-3-(4-pentynyl)imidazolium iodide,37 1-(propargyloxy-
methyl)pyrene,38 N-(propargyl)-4-amino-1,8-naphthalimide,23 9-pro-
1
6c. Yield: 90%. H NMR (250 MHz, CDCl3) δ = 7.49 (s, 1H),
7.40ꢀ7.20 (m, 5H), 4.61 (s, 2H), 4.33 (t, J = 7.2 Hz, 2H), 3.81 (q, J = 7.0
Hz, 6H), 3.51 (br, 2H), 2.09ꢀ1.92 (m, 2H), 1.21 (t, J = 7.0 Hz, 9H),
0.65ꢀ0.55 (m, 2H). (4H missing). 13C NMR (100 MHz, CDCl3)
δ = 144.3, 131.8, 128.1, 122.5, 64.3, 58.2, 52.2, 23.9, 18.0, 7.3. (3C
missing). HRMS (ESI+): calcd for C21H37N4O5Si 453.2533, found
453.2540.
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6d. Yield: 91%. 1H NMR (400 MHz, CDCl3) δ = 10.18 (s, 1H), 7.65
(d, J = 1.5 Hz, 1H), 7.63 (s, 1H), 7.62 (d, J = 1.5 Hz, 1H), 4.46 (t, J = 7.0
Hz, 2H), 4.36ꢀ4.28 (m, 4H), 3.79 (q, J = 7.0 Hz, 6H), 2.78 (t, J = 7.0 Hz,
2H), 2.40ꢀ2.33 (m, 2H), 2.03ꢀ1.95 (m, 2H), 1.45ꢀ1.31 (m, 4H), 1.19
(t, J = 7.0 Hz, 9H), 0.95 (t, J = 7.4 Hz, 3H), 0.61ꢀ0.55 (m, 2H). 13C
NMR (100 MHz, CDCl3) δ = 145.3, 123.0, 122.3, 121.9, 58.6, 52.6, 50.1,
49.1, 32.2, 30.0, 24.3, 21.9, 19.6, 18.4, 13.5, 7.6. HRMS (ESI+): calcd for
C21H40N5O3Si 438.2900, found 438.2881.
13C NMR (100 MHz, CDCl3) δ = 158.6, 146.3, 122.2, 62.4, 58.2, 50.2,
42.8, 35.1, 32.6, 30.0, 29.4, 29.3, 29.23, 29.18, 28.8, 26.3, 25.7, 23.5, 18.2,
7.5. HRMS (ESI+): calcd for C24H50N5O5Si 516.3581, found 516.3558.
7e. Yield: 83%. 1H NMR (400 MHz, CDCl3) δ = 8.22ꢀ7.94
(m, 8H), 7.85 (d, J = 7.8 Hz, 1H), 7.34 (s, 1H), 6.08 (s, 2H), 5.65 (t, J =
5.6 Hz, 1H), 5.08 (t, J = 5.4 Hz, 1H), 4.30 (d, J = 5.8 Hz, 2H), 3.75 (q, J =
7.0 Hz, 6H), 3.11ꢀ3.04 (m, 2H), 1.58ꢀ1.49 (m, 2H), 1.16 (t, J = 7.0 Hz,
9H), 0.60ꢀ0.54 (m, 2H). 13C NMR (100 MHz, CDCl3) δ = 158.2,
132.1, 131.2, 130.5, 129.2, 129.0, 128.3, 127.7, 127.2, 126.8, 126.4, 125.9,
125.8, 125.1, 125.0, 124.5, 121.9, 58.4, 52.4, 43.0, 35.6, 23.6, 18.4, 7.7
(1C missing). HRMS (ESI+): calcd for C30H38N5O4Si 560.2693, found
560.2693.
6e. Yield: 95%. 1H NMR (400 MHz, CDCl3) δ = 8.31 (d, J = 9.2 Hz,
1H), 8.19ꢀ8.06 (m, 4H), 8.05ꢀ7.94 (m, 4H), 7.50 (s, 1H), 5.28 (s, 2H),
4.80 (s, 2H), 4.30 (t, J = 7.2 Hz, 2H), 3.80 (q, J = 7.0 Hz, 6H), 2.05ꢀ1.95
(m, 2H), 1.20 (t, J = 7.0 Hz, 9H), 0.63ꢀ0.56 (m, 2H). 13C NMR (100
MHz, CDCl3) δ = 145.1, 131.4, 131.2, 131.0, 130.8, 129.4, 127.8, 127.5,
127.4, 127.2, 125.9, 125.2 (2C), 124.9, 124.7, 124.5, 123.4, 122.6, 71.0,
63.8, 58.5, 52.4, 24.2, 18.3, 7.5. HRMS (ESI+): calcd for C29H36N3O4Si
518.2475, found 518.2453.
7f. Yield: 93%. 1H NMR (400 MHz, CDCl3) δ = 8.33 (br, 1H), 7.86
(br, 1H), 7.62 (s, 1H), 6.05 (br, 2H), 5.54 (br, 1H), 5.09 (br, 1H), 4.41
(d, J = 5.6 Hz, 2H), 4.34 (t, J = 6.4 Hz, 2H), 4.24 (t, J = 6.3 Hz, 2H), 3.79
(q, J = 7.0 Hz, 6H), 3.18ꢀ3.11 (m, 2H), 2.57ꢀ2.48 (m, 2H), 1.64ꢀ1.54
(m, 2H), 1.19 (t, J = 7.0 Hz, 9H), 0.64ꢀ0.58 (m, 2H). 13C NMR (100
MHz, CDCl3) δ = 158.4, 155.8, 153.2 132.1, 122.5, 58.6, 47.2, 43.1, 41.1,
35.8, 30.2, 23.7, 18.4, 7.8 (2C missing). HRMS (ESI+): calcd for
C21H37N10O4Si 521.2769, found 521.2769.
6f. Yield: 68%. 1H NMR (250 MHz, DMSO) δ = 8.63 (d, J = 8.2 Hz,
1H), 8.43 (d, J = 7.1 Hz, 1H), 8.19 (d, J = 8.4 Hz, 1H), 7.94 (s, 1H), 7.66
(t, J = 7.8 Hz, 1H), 7.49 (s, 2H), 6.84 (d, J = 8.4 Hz, 1H), 5.25 (s, 2H),
4.24 (t, J = 6.9 Hz, 2H), 3.66 (q, J = 7.0 Hz, 6H), 1.86ꢀ1.70 (m, 2H),
1.07 (t, J = 7.0 Hz, 9H), 0.48ꢀ0.37 (m, 2H). 13C NMR (100 MHz,
CDCl3) δ = 164.5, 163.7, 151.1, 144.1, 134.0, 131.2, 129.6, 128.3, 124.2,
123.3, 122.1, 119.7, 109.9, 108.9, 58.6, 52.6, 34.9, 24.3, 18.3, 7.6. HRMS
(ESI+): calcd for C24H32N5O5Si 498.2173, found 498.2166.
7g. Yield: 96%. 1H NMR (400 MHz, CDCl3) δ = 7.55 (s, 1H), 6.01
(br, 1H), 5.32 (br, 1H), 4.38 (d, J = 5.7 Hz, 2H), 4.27 (t, J = 7.3 Hz, 2H),
3.76 (q, J = 7.0 Hz, 6H), 3.75 (q, J = 7.0 Hz, 6H), 3.16ꢀ3.09 (m, 2H),
2.01ꢀ1.91 (m, 2H), 1.60ꢀ1.51 (m, 2H), 1.17 (t, J = 7.0 Hz, 9H), 1.16
(t, J = 7.0 Hz, 9H), 0.62ꢀ0.53 (m, 4H). 13C NMR (100 MHz, CDCl3)
δ = 158.5, 146.3, 122.4, 58.6, 58.4, 52.6, 43.0, 35.4, 24.2, 23.7, 18.3 (2 C),
7.7, 7.6. HRMS (ESI+): calcd for C22H48N5O7Si2 550.3092, found
550.3083.
6g. Yield: 94%. 1H NMR (400 MHz, CDCl3) δ = 7.45 (s, 1H), 4.67
(t, J = 1.5 Hz 2H), 4.31 (t, J = 7.1 Hz, 2H), 4.24 (t, J = 1.5 Hz, 2H), 4.03
(s, 5H), 3.78 (q, J = 7.0 Hz, 6H), 2.04ꢀ1.96 (m, 2H), 1.19 (t, J = 7.0 Hz,
9H), 0.61ꢀ0.54 (m, 2H). 13C NMR (100 MHz, CDCl3) δ = 146.4,
118.9, 75.7, 69.5, 68.6, 66.6, 58.6, 52.3, 24.2, 18.3, 7.4. HRMS (ESI+):
calcd for C21H32N3O3FeSi 458.1562, found 458.1552.
7h. Yield: 90%. 1H NMR (250 MHz, CDCl3) δ = 7.45 (s, 2H), 7.23
(s, 4H), 5.55ꢀ5.35 (m, 6H), 4.99 (br, 2H), 4.37 (d, J = 5.6 Hz, 4H), 3.79
(q, J = 7.0 Hz, 12H), 3.17ꢀ3.06 (m, 4H), 1.63ꢀ1.50 (m, 4H), 1.20 (t, J =
7.0 Hz, 18H), 0.64ꢀ0.56 (m, 4H). 13C NMR (100 MHz, CDCl3)
δ = 158.4, 135.4, 128.9, 58.6, 53.7, 43.1, 35.7, 23.7, 18.4, 7.7 (2C missing).
7i. Yield: 91%. 1H NMR (400 MHz, CDCl3) δ = 7.56 (s, 2H), 6.18
(br, 2H), 5.46 (br, 2H), 4.37 (d, J = 4.9 Hz, 4H), 4.25 (t, J = 7.0 Hz, 4H),
3.75 (q, J = 7.0 Hz, 12H), 3.15ꢀ3.08 (m, 4H), 1.86ꢀ1.78 (m, 4H),
1.60ꢀ1.50 (m, 4H), 1.29ꢀ1.09 (m, 30H), 0.61ꢀ0.55 (m, 4H). 13C
NMR (100 MHz, CDCl3) δ = 158.7, 146.4, 122.3, 58.4, 50.4, 43.0, 35.4,
30.1, 28.9, 28.6, 26.3, 23.7, 18.3, 7.7.
6h. Yield: 96%. 1H NMR (400 MHz, CDCl3) δ = 8.37 (s, 1H), 7.99
(s, 1H), 7.65 (s, 1H), 5.73 (br, 2H), 5.48 (s, 2H), 4.31 (t, J = 7.2 Hz, 2H),
3.78 (q, J = 7.0 Hz, 6H), 2.03ꢀ1.93 (m, 2H), 1.19 (t, J = 7.0 Hz, 9H),
0.59ꢀ0.53 (m, 2H). 13C NMR (100 MHz, CDCl3) δ = 155.6, 153.2,
150.0, 142.3, 123.0, 58.7, 52.7, 38.8, 24.3, 18.4, 7.6. (2C missing). HRMS
(ESI+): calcd for C17H29N8O3Si 421.2132, found 421.2132.
7a. Yield: 94%. 1H NMR (400 MHz, CDCl3) δ 7.49 (s, 1H),
7.38ꢀ7.30 (m, 3H), 7.27ꢀ7.19 (m, 2H), 5.84 (t, J = 5.7 Hz, 1H),
5.45 (s, 2H), 5.18 (t, J = 5.3 Hz, 1H), 4.38 (d, J = 5.9 Hz, 2H), 3.78 (q, J =
7.0 Hz, 6H), 3.17ꢀ3.10 (m, 2H), 1.62ꢀ1.53 (m, 2H), 1.18 (t, J = 7.0 Hz,
9H), 0.64ꢀ0.57 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 158.4, 146.8,
134.5, 129.2, 128.8, 128.2, 122.3, 58.5, 54.2, 43.0, 35.5, 23.6, 18.3, 7.7.
HRMS (ESI+): calcd for C20H34N5O4Si 436.2380, found 436.2397.
7b. Yield: 93%. 1H NMR (250 MHz, CDCl3) δ = 7.55 (s, 1H), 5.98
(br, 1H), 5.29 (br, 1H), 4.39 (d, J = 5.3 Hz, 2H), 4.27 (t, J = 7.3 Hz, 2H),
3.77 (q, J = 7.0 Hz, 6H), 3.18ꢀ3.09 (m, 2H), 1.90ꢀ1.79 (m, 2H),
1.63ꢀ1.50 (m, 2H), 1.34ꢀ1.22 (m, 6H), 1.18 (t, J = 7.0 Hz, 9H), 0.85 (t,
J = 6.5 Hz, 3H), 0.64ꢀ0.55 (m, 2H). 13C NMR (100 MHz, CDCl3)
δ = 158.7, 58.3, 50.3, 42.9, 35.3, 31.1, 30.1, 26.1, 23.7, 22.4, 18.3, 13.9, 7.6
(2C missing).
7j. Yield: 96%. 1H NMR (400 MHz, CDCl3) δ = 7.11 (s, 3H), 6.06
(br, 3H), 5.60ꢀ5.54 (m, 9H), 4.30 (d, J = 5.6 Hz, 6H), 3.76 (q, J = 7.0
Hz, 18H), 3.09ꢀ3.00 (m, 6H), 2.30 (s, 9H), 1.56ꢀ1.46 (m, 6H), 1.16 (t,
J = 7.0 Hz, 27H), 0.58ꢀ0.52 (m, 6H). 13C NMR (100 MHz, CDCl3)
δ = 158.7, 147.0, 139.6, 130.8, 121.1, 58.4, 48.9, 43.0, 35.7, 23.7, 18.4,
16.6, 7.7.
1
7k. Yield: 93%. H NMR (400 MHz, CDCl3) δ = 7.83ꢀ7.76 (m,
4H), 7.74 (s, 2H), 7.39 (t, J = 7.5 Hz, 2H), 7.26 (t, J = 7.6 Hz, 2H), 7.15
(d, J = 8.5 Hz, 2H), 6.22 (br, 2H), 5.87 (d, J = 14.8 Hz, 2H), 5.70 (d, J =
14.8 Hz, 2H), 5.55 (br, 2H), 4.40 (dd, J = 15.3 and 5.7 Hz, 2H), 4.37 (dd,
J = 15.3 and 5.7 Hz, 2H), 4.28 (d, J = 5.8 Hz, 2H), 4.23 (d, J = 5.8 Hz,
2H), 3.75 (q, J = 7.0 Hz, 12H), 3.19ꢀ3.02 (m, 4H), 2.92 (s, 6H),
1.61ꢀ1.51 (m, 4H), 1.15 (t, J = 7.0 Hz, 18H), 0.62ꢀ0.56 (m, 4H). 13C
NMR (100 MHz, CDCl3) δ = 158.6, 152.4, 146.9, 134.1, 130.6, 130.4,
128.7, 128.4, 127.6, 125.8, 125.7, 125.1, 122.6, 99.5, 58.4, 57.0, 50.4, 43.0,
35.6, 23.7, 18.3, 7.7.
7c. Yield: 94%. 1H NMR (250 MHz, CDCl3) δ = 7.62 (s, 1H), 5.84
(br, 1H), 5.28 (br, 1H), 4.59ꢀ4.46 (m, 2H), 4.37 (d, J = 4.9 Hz, 2H),
4.12ꢀ3.99 (m, 4H), 3.76 (q, J = 7.0 Hz, 6H), 3.16ꢀ3.06 (m, 2H),
2.45ꢀ2.29 (m, 2H), 1.61ꢀ1.48 (m, 2H), 1.27 (t, J = 7.1 Hz, 6H), 1.16 (t,
J = 7.0 Hz, 9H), 0.62ꢀ0.53 (m, 2H). 13C NMR (100 MHz, CDCl3) δ =
158.5, 146.6, 122.8, 62.2 (d, J = 6.5 Hz), 58.4, 44.5, 42.9, 35.5, 27.2 (d, J =
141 Hz), 23.7, 18.3, 16.4 (d, J = 6 Hz), 7.7. 31P NMR (162 MHz, CDCl3)
δ = 25.5. HRMS (ESI+): calcd for C19H41N5O7SiP 510.2513, found
510.2511.
7l. Yield: 89%. 1H NMR (400 MHz, CDCl3) δ = 7.73ꢀ7.35 (m,
8H), 7.28ꢀ7.09 (m, 5H), 6.98 (d, J = 8.2 Hz, 2H), 5.84 (br, 2H),
5.40 (br, 6H), 4.01 (br, 4H), 3.68 (q, J = 7.0 Hz, 12H), 2.88 (br, 4H),
1.40 (br, 4H), 1.09 (t, J = 7.0 Hz, 18H), 0.49ꢀ0.43 (m, 4H). 13C
NMR (101 MHz, CDCl3) δ = 158.7, 152.7, 146.1, 134.5, 132.1,
128.6, 128.2, 127.3, 124.9, 124.8, 123.8, 122.8, 114.9, 58.5, 45.8,
42.9, 23.7, 18.4, 10.4, 7.8. HRMS (ESI+): calcd for C48H69N10O10-
Si2 1001.4737, found 1001.4682.
7d. Yield: 96%. 1H NMR (400 MHz, CDCl3) δ = 7.52 (s, 1H), 6.30
(br, 1H), 5.56 (br, 1H), 4.30 (d, J = 5.5 Hz, 2H), 4.19 (t, J = 7.2 Hz, 2H),
3.69 (q, J = 7.0 Hz, 6H), 3.51 (t, J = 6.7 Hz, 2H), 3.13 (br, 1H),
3.09ꢀ3.02 (m, 2H), 1.82ꢀ1.73 (m, 2H), 1.57ꢀ1.35 (m, 4H),
1.30ꢀ1.13 (m, 14H), 1.10 (t, J = 7.0 Hz, 9H), 0.55ꢀ0.49 (m, 2H).
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FEATURED ARTICLE
8a. Yield: 94%. 1H NMR (400 MHz, CDCl3) δ 7.48 (s, 2H),
7.38ꢀ7.27 (m, 6H), 7.25ꢀ7.19 (m, 4H), 5.48 (s, 4H), 3.76 (q, J = 7.0
Hz, 6H), 3.68 (br, 4H), 2.46ꢀ2.41 (m, 2H), 1.66ꢀ1.56 (m, 2H), 1.17 (t,
J = 7.0 Hz, 9H), 0.57ꢀ0.51 (m, 2H). 13C NMR (100 MHz, CDCl3) δ
145.1, 134.9, 129.1, 128.5, 128.0, 123.0, 58.3, 56.5, 54.1, 47.7, 20.6, 18.3,
7.8. HRMS (ESI+): calcd for C29H42N7O3Si 564.3118, found 564.3109.
8b. Yield: 91%. 1H NMR (250 MHz, CDCl3) δ = 7.57 (s, 2H), 4.31
(t, J = 7.3 Hz, 4H), 3.79 (q, J = 7.0 Hz, 6H), 3.71 (s, 4H), 2.51ꢀ2.43 (m,
2H), 1.95ꢀ1.81 (m, 4H), 1.74ꢀ1.60 (m, 2H), 1.33ꢀ1.28 (m, 12H),
1.20 (t, J = 7.0 Hz, 9H), 0.85 (t, J = 6.7 Hz, 6H), 0.64ꢀ0.55 (m, 2H). 13C
NMR (100 MHz, CDCl3) δ = 144.4, 122.9, 58.4, 56.6, 50.3, 47.5, 31.2,
30.3, 26.2, 22.4, 20.6, 18.4, 13.9, 7.9. HRMS (ESI+): calcd for
C27H54N7O3Si 552.4057, found 552.4063.
3,30-Bis(azidomethyl)-2,20-bis(methoxymethoxy)-1,10-bi-
naphthalene (10). To a solution of 945 (3.17 g, 7.29 mmol) in toluene
(100 mL) were added methanesulfonyl chloride (4.58 g, 40.1 mmol)
and triethylamine (5.57 g, 55.0 mmol) at 0 °C. The solution was stirred
overnight at rt. DMF (75 mL) and sodium azide (2.08 g, 32 mmol) were
added, and the mixture was stirred for 6 h at 60 °C. The solvents were
evaporated, and the residue was dissolved in CH2Cl2 and extracted with
water and brine. The organic fraction was dried over MgSO4 and then
concentrated. The crude product was purified by column chromatogra-
phy on silica gel (CH2Cl2, 1% MeOH). The pure product 10 (2.82 g,
5.82 mmol) was obtained as a yellow liquid. Yield: 80%. 1H NMR (400
MHz, CDCl3) δ = 8.02 (s, 2H), 7.92 (d, J = 8.0 Hz, 2H), 7.48ꢀ7.42 (m,
2H), 7.32ꢀ7.28 (m, 2H), 7.18 (d, J = 7.9 Hz, 2H), 4.79 (d, J = 14.0 Hz,
2H), 4.68 (d, J = 14.0 Hz, 2H), 4.53 (d, J = 5.9 Hz, 2H), 4.48 (d, J = 5.9
Hz, 2H), 3.01 (s, 6H). 13C NMR (100 MHz, CDCl3) δ = 152.6, 134.1,
130.7, 130.0, 129.4, 128.3, 127.3, 126.1, 125.7, 125.5, 99.6, 57.0, 51.0.
3,30-Bis(azidomethyl)-1,10-binaphthalene-2,20-diol (11).
The protected binol 10 (1.05 g, 2.17 mmol) was dissolved in THF
(20 mL), and concentrated HCl (12 M, 8.8 mL) was added dropwise at
0 °C. After being stirred for 5 h at rt, the solution was extracted with
EtOAc and washed with water, saturated NaHCO3, and brine. After
drying over Na2SO4 and concentration, the residue was purified by
chromatography column on silica gel (CH2Cl2, 5% MeOH). Pure diol
8c. Yield: 84%. 1H NMR (250 MHz, CDCl3) δ = 7.59 (s, 2H), 4.30
(t, J = 7.2 Hz, 4H), 3.78 (q, J = 7.0 Hz, 6H), 3.70 (s, 4H), 3.60 (t, J = 6.6
Hz, 4H), 2.50ꢀ2.42 (m, 2H), 2.12ꢀ1.78 (m, 6H), 1.76ꢀ1.38 (m, 6H),
1.35ꢀ1.16 (m, 37H), 0.63ꢀ0.54 (m, 2H). 13C NMR (100 MHz,
CDCl3) δ = 143.9, 122.9, 62.1, 58.1, 56.2, 50.0, 47.2, 32.5, 30.0, 29.24,
29.16, 29.1, 29.0, 28.7, 26.2, 25.6, 20.3, 18.1, 7.5. HRMS (ESI+): calcd for
C37H74N7O5Si 724.5521, found 724.5520.
1
8d. Yield: 91%. H NMR (250 MHz, CDCl3) δ = 7.63 (s, 2H),
4.63ꢀ4.51 (m, 4H), 4.15ꢀ4.00 (m, 8H), 3.77 (q, J = 7.0 Hz, 6H), 3.68
(s, 4H), 2.50ꢀ2.30 (m, 6H), 1.71ꢀ1.56 (m, 2H), 1.29 (t, J = 7.1 Hz,
12H), 1.18 (t, J = 7.0 Hz, 9H), 0.61ꢀ0.52 (m, 2H). 13C NMR (100
MHz, CDCl3) δ = 144.5, 123.2, 61.9 (d, J = 6.5 Hz), 58.1, 56.3, 47.4,
44.2, 27.0 (d, J = 141 Hz), 20.4, 18.1, 16.2 (d, J = 6 Hz), 7.6. 31P NMR
(162 MHz, CDCl3) δ = 25.58. HRMS (ESI+): calcd for C27H56N7O9-
SiP2 712.3384, found 712.3374.
1
11 was obtained as a yellow oil (0.73 g, 1.84 mmol). Yield: 89%. H
NMR (400 MHz, CDCl3) δ = 8.00 (s, 2H), 7.92 (d, J = 8.0 Hz, 2H),
7.44ꢀ7.39 (m, 2H), 7.35ꢀ7.31 (m, 2H), 7.12 (d, J = 7.9 Hz, 2H), 4.67
(s, 4H). 13C NMR (100 MHz, CDCl3) δ = 151.1, 133.3, 131.2, 129.3,
128.7, 128.1, 124.8, 124.6, 124.2, 111.3, 50.8.
1
8e. Yield: 90% (Containing 0.5 eq of Et3N). H NMR (400 MHz,
CDCl3) δ = 8.34 (s, 2H), 7.97 (s, 2H), 7.75 (s, 2H), 6.64 (br, 4H), 4.36
(t, J = 6.1 Hz, 4H), 4.24 (t, J = 6.2 Hz, 4H), 3.78 (q, J = 7.0 Hz, 6H), 3.72
(s, 4H), 2.56ꢀ2.45 (m, 8H), 1.73ꢀ1.64 (m, 2H), 1.18 (t, J = 7.0 Hz,
9H), 1.00 (t, J = 7.2, 4H), 0.65ꢀ0.57 (m, 2H). 13C NMR (100 MHz,
CDCl3) δ = 156.1, 153.2, 150.2, 145.1, 128.5, 123.8, 119.9, 58.5, 57.1,
47.6, 46.9, 46.4, 40.9, 30.4, 20.8, 18.4, 11.8, 8.0. HRMS (ESI+): calcd for
C31H48N17O3Si 734.3895, found 734.3868.
’ ASSOCIATED CONTENT
Supporting Information. 1H and 13C NMR spectra of 3,
S
b
5, 6aꢀh, 7aꢀl, 8aꢀg, 10, and 11. This material is available free of
charge via the Internet at http://pubs.acs.org.
’ AUTHOR INFORMATION
1
8f. Yield: 92%. H NMR (400 MHz, CDCl3) δ = 8.20ꢀ7.95 (m,
16H), 7.75 (d, J = 7.8 Hz, 2H), 7.22 (s, 2H), 6.05 (s, 4H), 3.65 (q, J = 7.0
Hz, 6H), 3.57 (s, 4H), 2.34 (t, J = 4 Hz, 2H), 1.52ꢀ1.42 (m, 2H), 1.08 (t,
J = 7.0 Hz, 9H), 0.44ꢀ0.37 (m, 2H). 13C NMR (100 MHz, CDCl3)
δ = 145.2, 132.0, 131.2, 130.6, 129.1, 128.9, 128.2, 127.4, 127.3, 127.1,
126.4, 125.9, 125.8, 125.0, 124.9, 124.5, 122.9, 122.0, 58.2, 56.5, 52.3,
47.8, 20.3, 18.3, 7.7. HRMS (ESI+): calcd for C49H50N7O3Si 812.3744,
found 812.3714.
Corresponding Author
*E-mail: xavier.cattoen@enscm.fr; michel.wong-chi-man@
enscm.fr.
’ ACKNOWLEDGMENT
Financial support to K.B. from the French Embassy in Prague
and from Specific University Research (MSMT No. 21/2011) is
gratefully acknowledged. We also thank ENSCM, CNRS, and
ANR (CP2D MESORCAT) for funding.
8g. Yield: 88%. 1H NMR (250 MHz, CDCl3) δ = 7.56 (s, 2H), 4.29
(t, J = 7.2 Hz, 4H), 3.82ꢀ3.65 (m, 22H), 2.48ꢀ2.38 (m, 2H), 2.04ꢀ1.89
(m, 4H), 1.64 (br, 2H), 1.19ꢀ1.11 (m, 27H), 0.59ꢀ0.51 (m, 6H). 13C
NMR (100 MHz, CDCl3) δ = 144.3, 123.1, 58.5, 58.4, 56.6, 52.5, 47.5,
24.3, 20.7, 18.4, 18.3, 7.9, 7.6. HRMS (ESI+): calcd for C33H70N7O9Si3
792.4543, found 792.4557.
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