Carbene X[sbnd]H bond insertions catalyzed by copper(I) macrocyclic pyridine-containing ligand (PcL) complexes

Article abstract of DOI:10.1016/j.jorganchem.2017.02.027

A catalytic system comprising copper(I) and macrocyclic pyridine-containing ligands (Pc-L) proves capable of promoting carbene Si[sbnd]H bond insertions using diazo compounds as the carbene source. This catalytic system showed broad scope and a remarkable robustness as indicated by high TON numbers (up to 30000). Moreover, the use of enynones as carbene sources proved also feasible in hydrosilane insertion using this catalytic system. Finally, the insertion in O[sbnd]H and N[sbnd]H bonds of phenols and anilines, respectively, has been also demonstrated.

Full text of DOI:10.1016/j.jorganchem.2017.02.027

Accepted Manuscript
Carbene X-H bond insertions catalyzed by copper(I) macrocyclic pyridine-containing
ligand (PcL) complexes
Giorgio Tseberlidis, Alessandro Caselli, Rubén Vicente
PII:
S0022-328X(17)30111-0
10.1016/j.jorganchem.2017.02.027
JOM 19816
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 21 November 2016
Revised Date: 15 February 2017
Accepted Date: 16 February 2017
Please cite this article as: G. Tseberlidis, A. Caselli, R. Vicente, Carbene X-H bond insertions catalyzed
by copper(I) macrocyclic pyridine-containing ligand (PcL) complexes, Journal of Organometallic
Chemistry (2017), doi: 10.1016/j.jorganchem.2017.02.027.
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ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT
Carbene X–H Bond Insertions Catalyzed by
Copper(I) Macrocyclic Pyridine-Containing Ligand
(PcL) Complexes
Giorgio Tseberlidis,1,2 Alessandro Caselli* 2 and Rubén Vicente*1
1Departamento de Química Orgánica e Inorgánica, and Instituto Universitario de
Química Organometálica “Enrique Moles”, Universidad de Oviedo, c/ Julián Clavería
2
8, 33007, Oviedo (Spain) and Dipartimento di Chimica, Università degli Studi di
Milano and ISTM-CNR, Via Golgi 19, 20133 Milano (Italy)
* Corresponding author. Email: Rubén Vicente - vicenteruben@uniovi.es and
Alesandro Caselli - alessandro.caselli@unimi.it
Abstract
A catalytic system comprising copper(I) and macrocyclic pyridine-containing ligands
(Pc-L) proves capable of promoting carbene Si-H bond insertions using diazo
compounds as the carbene source. This catalytic system showed broad scope and a
remarkable robustness as indicated by high TON numbers (up to 30000). Moreover,
the use of enynones as carbene sources proved also feasible in hydrosilane insertion
using this catalytic system. Finally, the insertion in O-H and N-H bonds of phenols
and anilines, respectively, has been also demonstrated.
Keywords
Si–H bond insertions, diazoalkanes, macrocyclic ligands, copper complexes,
Pyridine-containing ligands

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Introduction
Macrocycles constitutes an important class of ligands in transition metal chemistry
since they can mimic the biological environment of various metalloenzymes or can
provide beneficial thermodynamic and kinetic properties to their metal complexes[1-6]
.
1,4,7,10-Tetraazacyclododecane scaffolds, normally referred as cyclen-type ligands,
have been widely employed as ligands for a variety of metals and applied in different
reactions[7-14]. By introducing a pyridine at one of the coordinating positions, flexibility
of the ligand can be altered affecting the coordination properties and the activity of a
given metal complex. In this sense, we have recently reported a flexible, scalable and
high-yielding synthesis of pyridine-containing cyclen-type ligands, including chiral non
reacemic ones, starting from inexpensive materials (PcL, Scheme 1)[15-18]. The
macrocyclic skeleton is obtained by the sequential assembly of an (enantiopure)
aziridine, an (enantipure) primary amine and a 2,6-disubstituted pyridine derivative.
Enantiopure aziridines are easily prepared in two steps using natural aminoacids as
chiral pool[19]. Consequently, we have also studied their coordination chemistry and
catalytic activity with copper(I)[20-23], among other metals[24-27]. Due to the relevance in
synthesis of reactions involving metal-promoted carbene transfer using diazo
compounds[28,29], a series of Cu(I)-PcL complexes was evaluated to assess their
catalytic competence in alkene cyclopropanation reactions. Indeed, various Cu(I)-PcL
complexes proved capable of promoting cyclopropanations in high yields and, in
some cases, high enantioselectivities, yet in moderate diastereoselectivity (Scheme
1).
Besides, the selective functionalization of X–H bonds, particularly those with high
bonding energies, constitutes appealing transformations with interest from synthetic
and theoretical perspectives. Electrophilic metal-carbene intermediates generated

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from diazocompounds enable the functionalization of strong X–H bonds under very
mild reaction conditions[30,31]. With the aim to expand the scope and selectivity of
Cu(I)-PcL complexes in carbene transfer reactions, we decide to evaluate them in
archetypal X–H bond functionalization reactions. Considering the relevance of silicon-
containing compounds[32-35], which can be used as versatile synthetic intermediates,
we selected the metal-promoted carbene insertion into Si–H bonds[36] to test the
activity and selectivity of the Cu(I)-PcL catalytic system. Herein, we disclose our
findings.
Scheme 1: Synthesis of pyridine-containing ligands (PcL) and their applications in
copper(I)-catalyzed cyclopropanations with diazo compounds (Ref. 22). ([Cu(I)] =
(CuOTf)2·C6H6)
Results and Discussion
At the outset, ethyl 2-diazo-2-phenylacetate (1a) and dimethyl(phenyl)silane (2a, 3.0
equiv.) served as benchmark substrates for the study of the reaction (Scheme 2).
The catalytic system comprising (CuOTf)2·C6H6 and ligand L1[20] showed

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competence to promote efficiently Si–H bond insertion under mild reaction conditions
(r.t, DCE, 18 h, slow addition of 1a over 2a during 1.5 h, see the Supporting
Information for details), affording compound 3a in 85% isolated yield and a
remarkably high product selectivity, since only residual amounts of alkenes arising
from dimerization of the carbene were detected. Heterogeneous system employing
1
bare (CuOTf)2·C6H6 in the absence of the ligand led to the formation of 3a (75%, H
NMR yield) along with alkenes by-products derived from diazo homocoupling (ca.
1
25%, H NMR yield). It should be noticed that the formation of these by-products
deleteriously impacts the practicality of the reaction since product isolation and
purification by standard techniques becomes unrealizable.
With this result in hands and based on our previous studies,[21-23] pseudo-C2-
symmetrical L2 ligand was used to assess the ability for a stereoselective Si–H
insertion[37-45]. Even though L2 kept similar yield efficiency, 3a was disappointingly
obtained as a racemate.
Scheme 2: Cu(I)/PcL-catalyzed carbene insertion in Si–H bonds: initial findings and
ligand evaluation. Isolated yields.

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As we earlier showed in cyclopropanation reactions[22], we believe that the
enantioselective outcome of the reaction is imposed preferentially by the presence of
the stereogenic carbon provided by the amine fragment (position 13, see
Experimental Section for numbering). Moreover, an overcrowded environment
around the metal might likely be detrimental for the selectivity of the carbene
transfer[46]
.
In fact, unsubstituted enantiopure ligand L3 provided 3a as a single reaction product
in excellent yield (92%) and with a promising 16% of ee. Noteworthy, ligand L3
provides complete product selectivity since dimers arising from diazo compounds 1a
1
were not detected in the reaction crude as judged by H NMR. Disappointingly,
among various modifications on the reaction conditions, the asymmetric induction
could be increased only to 46% ee at low temperature (–30 ºC) with a 5.0 mol%
catalyst loading (based on metal, for details on the screening, see the Supporting
Information).[14] It is worth mentioning that the corresponding catalytic system using
AgOTf as the metal source did not provide silane 3a[47]
.
Despite the modest values of ee obtained, we also tried to assess the scope of the
transformation using ligands L1 and L3. Thus, various diazo compounds were
subsequently tested, as depicted in Table 1. Indeed, various 2-aryl diazo compounds
could be employed to obtain the corresponding functionalized silanes 3a–g in good
yields. Neither the electronic properties nor the steric hindrance of the arene
influenced the yield. Modification on the ester of the diazo could be also
accomplished as demonstrated with the synthesis of silanes 3h–i. Noteworthy, a
diazo phosphonate could also be employed, yet higher temperature was required to
reach a useful yield preparing 3j. Unfortunately, the use of alkyl- or vinyl-substituted
diazo compounds seemed to be incompatible with this protocol. Commercially

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available ethyl diazoacetate was also employed in the reaction with triethylsilane,
leading to compound 3k almost quantitatively (96% yield) and, importantly, avoiding
the undesired homodimerization. With respect to the silane reagent, commonly
employed silanes, such as diphenylmethylsilane or triethylsilane were functionalized
in generally good yields (compounds 3l–m). It should be noticed that sterically
hindered silanes, as triphenylsilane or triisopropylsilane were well tolerated
(compounds 3n–o). The preparation in good yields of 3p–q by means of using
various hydrosiloxanes, which can be further modified, demonstrated the broad
scope of the transformation. Interestingly, by tuning the stoichiometry of diazo 1a and
1,1,3,3-tetramethyldisiloxane (TMDS, 2h) we were able to prepare mono- and
difunctionalized silanes 3r and 3s with very good overall yield and complete product
selectivity. It should be noticed that ligand L3 provided, in general, better yields of 3
than analogous L1, minimizing the formation of carbene dimerization side-products
(see below). As already noted before, copper(I) triflate in the absence of the ligand is
a competent catalyst for the diazoalkane activation but, especially with more hindered
substrates such as triphenylsilane, the carbene dimerization side-products are
formed preferentially. Neither the modifications on the arene of the diazo compounds
nor the substituents on the silane showed a decisive influence in the stereochemical
outcome of the reaction when L3 was used, providing low ee values (0-36% ee, see
Supporting Information for details).

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Table 1: Cu(I)/PcL-catalyzed Si–H bond carbene insertion: Scope.a

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a See Supporting Information for detailed reaction conditions. Isolated yields. b T = 70
ºC. c Diazo/silane ratio 5:1. 3s was obtained as a mixture of diastereoisomers.
In the recent years, the use of conjugated enynones as precursors of furyl carbene
intermediates has been fruitfully exploited by means of transition metal catalysis[48-50]
.
We wondered if the Cu(I)-PcL catalytic system could be used with this type of
carbenes for the Si–H insertion reaction. Indeed, when enynones 4 were treated with
silane 2a under the standard conditions, the corresponding 2-furylmethylsilanes 5a–b
were obtained in good yields, confirming the capability of the catalyst (Scheme 3).
Noteworthy, the formation of furyl-carbene dimerization products was also minimized
by using this catalytic system. Regrettably, no stereoselection was observed under
the conditions tested.
Scheme 3: Cu(I)/PcL-catalyzed Si-H bond carbene insertions using conjugated
enynones 4 as the carbene source. ([Cu(I)] = (CuOTf)2·C6H6).
In addition to the scope in Si–H bond insertion reactions, we also tested the
robustness of the catalytic system Cu(I)-PcL using L1 and L3 by performing the
model reaction at lower catalyst loadings (Scheme 4). Interestingly, a 100-fold
decrease in the catalyst loading with L1 ((CuOTf)2·C6H6 : 0.01 mol%; L1: 0.022
mol%), under otherwise identical reaction conditions (r.t, DCE, 18 h, slow addition of
1a over 2a during 1.5 h, see the Supporting Information for details), led to the

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1
formation of 3a in a useful 64% yield (68% conversion of 1a by H-NMR, 94%
selectivity). It should be pointed out at this stage that the same reaction in the
1
absence of added ligand resulted in a lower conversion (35% H NMR yield) and
product selectivity (a 3:1 ratio of 3a with respect to alkenes arising from carbene
dimerization was observed). A slow addition of the 1a was still required in order to
avoid the formation of dimerization products. A one order of magnitude diminution of
the catalyst loading revealed the formation of 3a in lower yield (27% yield, 36%
conv.). Moreover, the use of L3 at low catalyst loadings was also feasible. Indeed,
silane 3a was obtained in 85% yield by using 0.02 mol% of catalyst loading after 48 h
(>95% conv.). Further decrease in the loading to 0.002 mol%, resulted in a slower
reaction, nevertheless, a remarkable 60% yield of 3a was obtained after 84 h (70%
conv.), meaning a respectable TON number of 30000. At lower catalyst loading ee
values were also low (ca. 5%). Further decrease in the catalyst loading (0.0002
mol%) led to the formation of carbene dimerization products (20% NMR yield; 24%
conv.) without the observation of 3a. It is important to highlight the high product
selectivity of both catalytic systems, since small amounts of alkenes arising from
diazo homocouplings were detected in the reaction mixture. The remarkable stability
of the Cu(I) complex with ligand L3 can be ascribed to the macrocyclic structure of
the ligand and to the presence of a pendant naphthyl group, which can coordinate
(η
2) the copper(I) atom.[22]

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Scheme 4: Robustness of the catalytic system Cu(I)/PcL in Si-H bond carbene
insertions at low catalyst loadings.
Finally, we wondered if the present catalytic system could be able to promote other
typical X–H bond insertion reactions (Table 2)[30,31]. For instance, under the standard
reaction conditions (with L3), the reaction of diazo compound 2a with phenol (6a)
afforded the corresponding insertion product 7a in a good isolated yield of 83%,
albeit almost as a racemic mixture[51,52]. The catalytic system proved active both with
electron rich and electron poor phenols, leading to the corresponding ethers 7b-c in
reasonable yields. Additionally, the analogous transformation using aniline (7a) led to
the formation of secondary amine 9a in 81% isolated yield. In this case, EDG- or
EWG-substituted anilines were used to yield 9b-c in good yields[53-57]. Besides, with
ethyl diazoacetate the reaction proceeds smoothly and the O-H or the N-H inserted
products 7d or 9d were isolated in good yields. Unfortunately, aliphatic alcohols and
amines were unreactive when using this catalytic system.

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Table 2: Cu(I)/PcL-catalyzed X–H bond carbene insertion: Scope.a
a See Supporting Information for detailed reaction conditions. Isolated yields.
Conclusion
In summary, we have demonstrated the ability of the catalytic system comprising
Cu(I) and pyridine-containing ligands (PcL) to promote the insertion of carbene
intermediates into Si–H bonds. This catalytic system, comprised of an economic
metal source and an easy to assemble macrocyclic ligand, demonstrated a
remarkable ample scope and product selectivity. Moreover, the catalytic system is
quite robust and the remarkable TON of 30000 could be achieved. On the contrary,
the level of stereoinduction of the ligand was modest. As bonus features, this
catalytic system enabled the use of alternative carbene sources as conjugated
enynones, yielded to only very modest amounts of side products derived from diazo-
homocoupling, including those examples with less reactive substrates, and could be
employed for the insertions onto O–H and N–H bonds. The chemoselective insertion

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into N-H vs O-H bond has also been shown, despite the fact that a good reactivity of
the catalyst towards phenols has been observed. Studies towards the implementation
in the ligand structure with the aim to extend synthetic applications and increase the
stereoinduction capacity are currently ongoing in our labs.
Experimental
General Experimental Details
All reactions were carried out under an argon atmosphere using standard Schlenck
techniques. 1,2-Dichloroethane (DCE) was distilled form CaH2 under nitrogen
atmosphere. Solvents for column chromatography were obtained from commercial
supplier and used without further purification. TLC was performed on aluminum-
backed plates coated with silica gel 60 with F254 indicator. Flash column
1
chromatography was carried out on silica gel (230-240 mesh). H-NMR (300, 400
MHz) and 13C-NMR (75.5 and 100 MHz) spectra were recorded at room temperature
in CDCl3 on a Bruker DPX-300, or Bruker AVANCE-300 MHz and 400 MHz
instruments. Chemical shifts (δ) are given in ppm relative to TMS (1H, 0.0 ppm) or
CDCl3 (13C, 77.0 ppm). Carbon multiplicities were assigned by DEPT experiments.
High-resolution mass spectra were recorded in with a VG AutoSpec M mass
spectrometer. IR spectra were recorded at a Bruker Alpha-T IR spectrometer. Diazo
compounds 1[58], enynones 4[59], [Cu(OTf)]2·C6H6[60] and PcL-type ligands L1, L2 and
L3 were prepared according to literature procedures.[22] The rest of the compounds
were commercially available.

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Representative procedure for the Cu(I) catalyzed Si-H bond carbene
insertion using diazocompounds
Under Ar atmosphere, a solution of L1 or L3 (0.0044 mmol) and [(CuOTf)2ꢀC6H6)]
(0.002 mmol) in 1,2-dichloroethane (1.0 mL) was stirred for 1h at rt. The silane 2 (0.6
mmol) was added, followed by the slow addition during 1.5 h of a solution of the
diazocompound 1 (0.2 mmol) in 1,2-dichloroethane (1.0 mL) using a syringe pump.
The resulting mixture was stirred at this temperature until disappearance of the
starting material (checked by TLC analysis). The solvent was removed under
vacuum. The resulting residue was purified by flash column chromatography (SiO2,
hexanes:ethyl acetate) to afford 3.
Representative Procedure for the Cu(I) catalyzed Si-H bond carbene
insertion using enynones
Under Ar atmosphere, a solution of L3 (0.0044 mmoles) and [(CuOTf)2ꢀC6H6)] (0.002
mmoles) in 1,2-dichloroethane (1.0 mL) was stirred for 1h at rt. Silane 2a (0.6
mmoles) was added, followed by the slow addition during 1.5 h of a solution of the
enynone 4 (0.2 mmoles) in 1,2-dichloroethane (1.0 mL) using a syringe pump. The
resulting mixture was stirred at this temperature until disappearance of the starting
material (checked by TLC analysis). The solvent was removed under vacuum. The
resulting residue was purified by flash column chromatography (SiO2, hexanes:ethyl
acetate) to afford 5.
Representative procedure for the Cu(I) catalyzed X-H bond carbene
insertion using diazocompounds.
Under N2 atmosphere, a solution of L3 (0.0044 mmol) and [(CuOTf)2ꢀC6H6)] (0.002
mmol) in 1,2-dichloroethane (1.0 mL) was stirred for 1h at rt. The phenol 6 or the
aniline 8 (0.6 mmol) was added, followed by the slow addition during 1.5 h of a

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solution of the diazocompound 1 (0.2 mmol) in 1,2-dichloroethane (1.0 mL) using a
syringe pump. The resulting mixture was stirred at this temperature until
disappearance of the starting material (checked by TLC analysis). The solvent was
removed under vacuum. The resulting residue was purified by flash column
chromatography (SiO2, hexanes:ethyl acetate) to afford 7 or 9, respectively.
Supporting Information
Detailed experimental procedures, text, figures and tables reporting full NMR spectra
for all compounds This material is available free of charge via the Internet.
Supporting Information File 1: Detailed experimental procedures, text, figures and
tables reporting full NMR spectra for all compounds This material is available free of
charge via the Internet.
File Name: Supporting Information
File Format: pdf
Title: Carbene X–H Bond Insertions Catalyzed by Copper(I) Macrocyclic Pyridine-
Containing Ligand (PcL) Complexes
Acknowledgements
Financial support from Ministerio de Economía y Competitividad (MINECO,
CTQ2013-41511-P), Principado de Asturias (GRUPIN14-013) and Erasmus Life-
Learning Program (fellowship to G. T.) is gratefully acknowledged. R. V. is a Ramón
y Cajal fellow.
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ACCEPTED MANUSCRIPT
* Cu(I)-PcL complexes promote carbene insertion in Si-H bonds.
* Cu-PcL catalytic system shows broad scope and a notable robustness (up to 30000
TON).
* Cu-PcL promotes carbene insertions in O-H or N-H bonds of phenols and anilines.