Stereoselective Rh2(S-IBAZ)4-catalyzed cyclopropanation of alkenes, alkynes, and allenes: Asymmetric synthesis of diacceptor cyclopropylphosphonates and alkylidenecyclopropanes

Article abstract of DOI:10.1021/ja3099728

A mild and highly stereoselective rhodium(II)-catalyzed cyclopropanation of alkenes, alkynes, and allenes with diacceptor diazo compounds is reported. Using the phosphonate moiety as an efficient trans-directing group, the first catalytic asymmetric route to diacceptor cycloprop(en)ylphosphonates was developed by employing an α-cyano diazophosphonate and Rh ₂(S-IBAZ)₄ as chiral catalyst. The isosteric character of phosphonic and carboxylic acid derivatives allowed the alternative use of an α-cyano diazo ester in the process, leading to α-cyano cycloprop(en)ylcarboxylates in high yields and stereoselectivities. Taking advantage of the particular reactivity of the cyanocarbene intermediates involved in this system, the scope of compatible substrates could be extended to substituted allenes, leading to the development of the first catalytic enantioselective method for the synthesis of diacceptor alkylidenecyclopropanes.

Full text of DOI:10.1021/ja3099728

Article
pubs.acs.org/JACS
Stereoselective Rh2(S‑IBAZ)4‑Catalyzed Cyclopropanation of Alkenes,
Alkynes, and Allenes: Asymmetric Synthesis of Diacceptor
Cyclopropylphosphonates and Alkylidenecyclopropanes
Vincent N. G. Lindsay,‡ Dominic Fiset,‡ Philipp J. Gritsch,† Soula Azzi, and Andre B. Charette*
́
Centre in Green Chemistry and Catalysis, Department of Chemistry, Universite
Montreal, Quebec, Canada H3C 3J7
́ ́
de Montreal, P.O. Box 6128, Station Downtown,
́
́
S
* Supporting Information
ABSTRACT: A mild and highly stereoselective rhodium(II)-catalyzed cyclopropanation of alkenes, alkynes, and allenes with
diacceptor diazo compounds is reported. Using the phosphonate moiety as an efficient trans-directing group, the first catalytic
asymmetric route to diacceptor cycloprop(en)ylphosphonates was developed by employing an α-cyano diazophosphonate and
Rh2(S-IBAZ)4 as chiral catalyst. The isosteric character of phosphonic and carboxylic acid derivatives allowed the alternative use
of an α-cyano diazo ester in the process, leading to α-cyano cycloprop(en)ylcarboxylates in high yields and stereoselectivities.
Taking advantage of the particular reactivity of the cyanocarbene intermediates involved in this system, the scope of compatible
substrates could be extended to substituted allenes, leading to the development of the first catalytic enantioselective method for
the synthesis of diacceptor alkylidenecyclopropanes.
Scheme 1. Enantioselective Synthesis of
Cyclopropylphosphonates and ACPs via the Metal-Catalyzed
Decomposition of Diazo Compounds
INTRODUCTION
■
The cyclopropylphosphonate unit is found in numerous natural
or synthetic compounds of pharmaceutical interest.1 Because of
their increased resistance to enzymatic hydrolysis, phospho-
nates and other phosphonic acid derivatives are often employed
in medicinal chemistry as isosteres of carboxylates2 and
phosphates.3 The ubiquity of the cyclopropylcarboxylate unit
in biologically relevant compounds has thus motivated several
research groups to study cyclopropylphosphonates as active
analogues, affording improved pharmaceutical properties in
certain cases.4
In analogy to cyclopropylcarboxylates,5 the most efficient
catalytic asymmetric methods for their formation involves the
reaction of a monoacceptor diazophosphonate species with an
alkene using chiral copper(I),6 ruthenium(II),6,7 or rhodium-
(II)8 catalysts (Scheme 1a).9 However, the enantioselective
synthesis of the corresponding diacceptor cyclopropylphospho-
nates using such a strategy remains unexplored.10,11 Because of
the high potential of diacceptor cyclopropanes in asymmetric
synthesis, either as precursors of ACC derivatives,12 or as
substrates in stereospecific substitution12d,13 and formal
cycloaddition reactions,14 we envisioned that access to their
phosphonate-substituted analogues in enantioenriched form
would be of considerable value. Herein, we describe the first
catalytic asymmetric synthesis of diacceptor cycloprop(en)-
ylphosphonate derivatives, using an α-cyano diazophosphonate
reagent and Rh2(S-IBAZ)4 as chiral catalyst, under mild
reaction conditions (Scheme 1b). The isosteric character of
carboxylates and phosphonates permitted the extension of the
Received: October 9, 2012
Published: January 4, 2013
© 2013 American Chemical Society
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scope of enantioenriched products to α-cyano cyclopropylcar-
boxylates under similar reaction conditions. Importantly, these
findings enabled the development of the first catalytic
asymmetric cyclopropanation of allenes using diacceptor
diazo compounds, leading to a variety of highly enantioenriched
alkylidenecyclopropanes (ACPs). Considering the importance
of diacceptor cyclopropanes and ACPs as synthetic inter-
mediates in a vast array of transformations, these methods are
of broad applicability for the stereoselective synthesis of
complex molecules.
Table 1. Optimization of the Nature of the Catalyst and the
Diazophosphonate Substrate
a
b
entry
R1
Rh(II) catalyst
yield (%) dr (t:c)
ee (%)
a
1
Et (4)
Rh2(OAc)4
58
65
72
24
44
81
84
84
99
73
79
76
47
36
52
99
83:17
87:13
90:10
75:25
73:27
88:12
87:13
89:11
89:11
84:16
76:24
78:22
92:8
−
−
−
−
−
−
−
−
a
a
a
a
a
a
a
f
2
3
4
5
6
7
8
9
Ph (5)
Rh2(OAc)4
RESULTS AND DISCUSSION
i-Pr (6)
i-Pr (6)
i-Pr (6)
i-Pr (6)
i-Pr (6)
i-Pr (6)
i-Pr (6)
i-Pr (6)
i-Pr (6)
i-Pr (6)
i-Pr (6)
i-Pr (6)
i-Pr (6)
i-Pr (6)
Rh2(OAc)4
■
Rh2(tpa)4
Stereoselective Cyclopropanation of Diacceptor Diaz-
ophosphonates. Recently, our group has been interested in
the use of diacceptor diazo compounds in stereoselective metal-
catalyzed cyclopropanation reactions.12,15 In such processes,
both electron-withdrawing substituents of the substrate
compete for their trans-directing abilities, which depend upon
steric and electronic factors.12d,15a Thus, to obtain a reasonable
diastereoselectivity ratio in those reactions, the steric and/or
basicity difference of the two groups in play has to be
significant. Moreover, the resulting combination of EWGs must
lead to an electrophilic, yet sterically accessible, reactive metal−
carbene species. Due to the inherent steric congestion of the
phosphonate moiety as trans-directing group, the small and
strongly electron-withdrawing cyano group was rapidly
identified as ideal in such cyclopropanation using diacceptor
diazophosphonates.16 Moreover, the established versatility of
diacceptor cyanocyclopropanes ensures considerable synthetic
divergence of the resulting enantioenriched α-cyano cyclo-
propylphosphonates.12d,16b,17
Rh2(tfa)4
Rh2(esp)2
Rh2(OPiv)4
Rh2(Adc)4
c e
−
Rh2(Adc)4
−
e
f
10
11
12
13
14
15
16
Rh2(S-NTTL)4
Rh2(S-PTTL)4
Rh2(S-TCPTTL)4
Rh2(S-MEAZ)4
Rh2(S-BNAZ)4
Rh2(S-IBAZ)4
Rh2(S-IBAZ)4
<5
33
<5
82
86
90
99
e
e
f
f
f
f
94:6
f
93:7
deg
, ,
f
97:3
a
b
Determined by 1H NMR analysis of the crude mixture. Determined
by SFC analysis on chiral stationary phase (ee of trans product).
c
d
Using 1,2-DCE as solvent. Using 1.5 equiv of 3 and 1 equiv of
e
f
styrene. 1 mol % catalyst used. Isolated yield of combined
diastereomers. Using degassed PhH as solvent at room temperature.
g
To maximize the yield and diastereoselectivity of the
reaction, the nature of the phosphonate and the achiral catalyst
used was first investigated in the reaction with styrene (Table 1,
entries 1−9, and Figure 1). Although substrates 2 and 3
afforded similar results in the reaction with Rh2(OAc)4 as
catalyst, the increased accessibility of 3 in addition to the
usefulness of dialkylphosphonates such as 6 convinced us to
continue our investigation with this substrate.17,18 While all
achiral Rh(II)-tetracarboxylate catalysts evaluated provided
complete consumption of the starting diazo compound,
Rh2(tfa)4 and Rh2(tpa)4 afforded only poor yields of 6 due to
undesired side reactions affording a complex mixture of
19
products (entries 4 and 5). The use of Rh2(Adc)4 proved
Figure 1. Structure of Rh(II) catalysts investigated.
to be optimal in those conditions with 84% yield and 89:11 dr,
and adding a slight excess of the diazo compound 3 with
styrene as limiting reagent was found to be crucial, resulting in a
99% isolated yield of 6 when 1,2-DCE was used as solvent
(entries 8 and 9).
cyclopropanation reactions using diazo compounds,5 both our
protocols do not require syringe-pump techniques or a large
excess of one of the reagents. Indeed, α-cyano diazophosph-
onate 3 (1.5 equiv) is added within 5−10 min via syringe to the
mixture containing the alkene (1 equiv) and the catalyst (1 mol
%) in solution.
Using the optimized conditions, a wide variety of terminal
alkenes were evaluated as substrates in our reaction, leading to
an unexpected generality for this type of process (Table 2,
entries 1−14).
Indeed, both electron-rich and -poor styrene derivatives,
substituted either at the ortho, meta, or para positions, all
provided excellent yields and stereoselectivities for the synthesis
of the corresponding racemic (conditions A) and enantioen-
riched (conditions B) diacceptor cyclopropylphosphonates
(entries 1−8). Moreover, heterocyclic derivative N-tosyl-3-
vinylindole was found to be compatible in the process, in
With these conditions in hand, various chiral catalysts were
evaluated in view of an enantioselective version of the reaction
(Table 1, entries 10−16). While the more traditional chiral
Rh(II)-tetracarboxylate catalysts afforded only poor stereo-
control (entries 10−12), the use of carboxamidate ligands,
more particularly azetidinates first developed by Doyle,20
permitted isolation of 6 in excellent enantioselectivity, although
with a lower yield (entries 13−15). Using styrene as limiting
reagent in a degassed solvent permitted to drastically improve
the yield of the reaction, affording optimal stereocontrol in
PhH at room temperature (entry 16). Under these conditions,
cyclopropane 6 was reproducibly obtained in 99% isolated
yield, 97:3 dr and 99% ee, using only 1 mol % of Rh2(S-IBAZ)4
as catalyst. It is noteworthy that unlike most metal-catalyzed
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Table 2. Scope of the Stereoselective Cyclopropanation Using α-Cyano Diazophosphonate 3
a
b
c
1
Isolated yield of combined diastereomers. Determined by H NMR analysis of the crude mixture. Determined by SFC analysis on chiral
d
stationary phase (ee of trans product). Using 3 equiv of substrate 3 and 2 mol % of the catalyst (reaction time: 60 h).
addition to a diene and an aliphatic olefin, in excellent
enantioselectivity (entries 9−11). The use of electron-poor
methylacrylate afforded a good yield under conditions A,
whereas only 17% of product 17 was obtained when Rh2(S-
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IBAZ)4 was used, presumably due to a lower electrophilicity of
the carbene intermediate with such rhodium(II) tetracarbox-
amidate catalyst (conditions B, entry 12).5a The use of Michael
acceptors as substrates is unprecedented in Rh(II)-catalyzed
cyclopropanation reactions, as only Co(II) carbenoids were
previously found to allow electron-poor alkenes to react with
the electrophilic metal−carbene intermediate.16b,21 Addition-
ally, the use of vinylbenzoate and N-vinylphthalimide as
substrates lead, respectively, to the formation of protected
cyclopropanol 18 and cyclopropylamine 19 in high yields and
stereoselectivities (entries 13 and 14). 1,1-Disubstituted alkenes
were also found to be compatible under our reaction
conditions, although only poor diastereoselectivity was
observed in the case of α-methylstyrene (Table 2, entries 15
and 16). Nevertheless, it should be noted that almost all
mixtures of diastereomers presented in Table 2 were separable
by flash chromatography. Conditions A provided high yields
and stereoselectivity with both cis and trans 1,2-disubstituted
alkenes, while the use of Rh2(S-IBAZ)4 under conditions B, a
more electron-rich catalyst, led to an important decrease in
yield of the corresponding diacceptor 1,1,2,3-tetrasubstituted
cyclopropanes 22 and 23 (entries 17 and 18).
Table 3. Rh2(S-IBAZ)4-Catalyzed Cyclopropanations with α-
Cyano Diazo Ester 29
Importantly, both conditions developed were successfully
applied to various terminal alkynes, leading to the correspond-
ing diacceptor cyclopropenylphosphonates 24−27 in good
yields and excellent stereoselectivity (Table 2, entries 19−22).
Cyclopropenes substituted by either an aromatic or an aliphatic
group are obtained with similar efficiency (24, 25, and 27), and
chemoselectivity for an alkyne over an alkene can be achieved
when using an enyne possessing an endocyclic double bond
(see 26, entry 21). It is noteworthy that the enantioselective
formation of diacceptor cyclopropenes through a metal-
catalyzed process is extremely rare in the literature.22,23 As
typically seen in Rh(II) catalysis,23k−n,24 1,2-disubstituted
alkynes were found to be incompatible in our system because
of the inherent paddlewheel structure of these complexes,
forbidding the approach of such substrates on the metal−
carbene intermediate (entry 23).
a
b
1
Isolated yield of combined diastereomers. Determined by H NMR
c
analysis of the crude mixture. Determined by SFC analysis on chiral
stationary phase (ee of trans product). Yield of pure trans
diastereomer.
d
Application to the Synthesis of Enantioenriched
Diacceptor Cyclopropylcarboxylate Derivatives. Cogni-
zant of the isosteric character of phosphonic and carboxylic acid
derivatives,2,3 we envisioned that α-cyano diazophosphonate 3
could be replaced by an α-cyano diazo ester such as 29 in our
system (Table 3). Indeed, the analogous steric profiles of both
metal−carbenes should lead to similar enantioinduction
mechanisms when using Rh2(S-IBAZ)4 as catalyst. In such a
situation, the hindered tert-butyl ester moiety acts as an efficient
trans-directing group, leading to the formation of the
corresponding trans-α-cyano cyclopropylcarboxylate product
in high yield and stereoselectivity, either with an aromatic or an
aliphatic olefin (entries 1 and 2). It is noteworthy that the
optimal conditions had to be slightly modified with 29, where
mesitylene was added in the solvent mixture to allow a
homogeneous reaction at the optimal temperature of 0 °C.
Moreover, the high reactivity of our system permitted the
extension of the scope of accessible enantioenriched products
to cyclopropenes 32 and 33 by reaction with phenylacetylene
and phenethylacetylene, respectively (entries 3 and 4). Despite
the low propensity of allenes to undergo cyclopropanation
reactions, we were delighted to observe the formation of E-
alkylidenecyclopropane 34 in excellent yield and enantiose-
lectivity (Table 3, entry 5, and Figure 2).25 While a vast array of
catalytic methods exist for the enantioselective synthesis of
Figure 2. X-ray structure of alkylidenecyclopropane 34.
cyclopropanes and cyclopropenes from diazo compounds,5 the
corresponding alkylidenecyclopropanation reactions remain
underexploited. In fact, this constitutes the first example of a
catalytic enantioselective alkylidenecyclopropanation reaction
using a diacceptor diazo compound.
Stereoselective Alkylidenecyclopropanation Reac-
tions. Because of the high potential of alkylidenecyclopropanes
(ACPs) as synthetic intermediates,26 we decided to further
investigate on this type of cyclopropanation involving allenes as
substrates. ACPs bearing electron-withdrawing groups are
known to exhibit an enhanced reactivity in multiple ionic
ring-opening processes, due to their increased ability to stabilize
a negatively charged open intermediate. Consequently, the
versatility of this type of substrate has been explored in various
reactions such as cycloisomerizations,27 ring-opening rearrange-
ments,28 cycloadditions,29 and iodolactonizations.30 Reported
syntheses of racemic diacceptor ACPs rely on cyclopropanation
of allenes,31 tandem addition-cyclization onto bromoallenes,32
intramolecular palladium-catalyzed cyclopropropanative aryla-
tion,29c and olefin migration.33 While Gregg reported an elegant
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asymmetric rhodium-mediated cyclopropanation of allenes with
aryldiazoacetate,34 no catalytic enantioselective method has
been described for the synthesis of diacceptor ACPs, which has
prohibited their use as chiral precursors for stereospecific
reactions.
In light of this, we investigated the scope of accessible
racemic products using phenylallene as substrate with a variety
of diacceptor diazo reagents (Table 4). Presumably due to the
Table 4. Alkylidenecyclopropanation of Phenylallene with
Various Diacceptor Diazo Reagents
ab
,
entry
EWG1
CO2t-Bu
EWG2
product
yield (%)
Figure 3. Possible conformations of (a) NO2- or C(O)R-substituted
metal−carbenes and (b) CN-substituted metal−carbenes.
1
CN
34
44
45
46
47
48
49
50
51
52
53
93
82
85
42
49
0
2
CO2Et
CN
3
CO2Ad
CN
with Rh(II) catalysts, only diazoacetonitrile derivatives are
compatible with less nucleophilic aliphatic alkenes as substrates,
also suggesting that the corresponding metal−carbene inter-
mediate is more electrophilic when substituted with a cyano
group.12d,15b
4
C(O)PMP
C(O)N(C4H8)
P(O)(Oi-Pr)2
CO2Et
CN
5
CN
6
CN
7
NO2
NO2
CO2Me
CO2Me
CO2Me
0
8
C(O)PMP
C(O)PMP
C(O)N(C4H8)
0
These studies thus permitted us to identify α-cyano diazo
ester 29 as an ideal substrate for the stereoselective Rh(II)-
catalyzed alkylidenecyclopropanation of phenylallene. To
explore the scope of accessible diacceptor ACPs in our system,
various allenes were evaluated as substrates, using either
Rh2(OPiv)4 (conditions A) or Rh2(S-IBAZ)4 (conditions B)
as catalysts, providing access to both racemic and enantioen-
riched products, respectively (Table 5). Modification of the
aromatic group’s electronic properties through the use of
differently substituted phenylallenes did not significantly affect
the stereoselectivity, as 95−97% ee was observed in all cases
(entries 1−5). Gratifyingly, various aliphatic allenes were also
well-tolerated, affording good yields and stereoselectivities for
the corresponding ACPs 58 and 59 with both methods (entries
6 and 7). Additionally, the presence of an N-phthaloyl group
directly on the allene moiety was found to be compatible,
though a lower isolated yield was observed under conditions B
(entry 8). Although a reasonable amount of the product was
isolated when ethyl allenoate was used, the electron-with-
drawing nature of the ester moiety, affording a less nucleophilic
allene, led to a significant decrease in the observed yield (entry
9). Importantly, the more sterically hindered 1,1-disubstituted
allenes were also reactive in both processes, and the presence of
a trimethylsilyl group considerably improved the reaction yield,
presumably via a β-silicon effect enhancing the allene’s
nucleophilicity (entries 10 and 11).31b,34 For all aromatic
allenes evaluated, only the E alkene of the product was
observed, while some of the Z diastereomer of 58, 60, and 61
9
<5
0
10
11
CO2Me
0
a
b
Isolated yield. Only one diastereoisomer was observed in all cases.
low nucleophilicity of allenes, only the most reactive cyano-
substituted carbenes provided useful amounts of the corre-
sponding alkylidenecyclopropane products, with α-cyano diazo
ester 29 affording the highest isolated yield (entries 1−5).
Indeed, although other diazo compounds substituted by either
NO2 or CO2Me groups were previously found to be competent
carbene precursors with styrene derivatives,12,15 no desired
product was observed with these reagents when phenylallene
was used (entries 7−11).
This increased reactivity of cyano-substituted carbenes can be
attributed to the inability of the sp-hybridized nitrile moiety to
adopt an out-of-plane conformation (Figure 3). The in-plane
conformation is believed to be highly energetic due to a
conjugation of the electrophilic metal carbene to an electron-
withdrawing group, and the out-of-plane conformation
represents the ground state of this reactive species. While
NO2 or C(O)R substituted metal−carbene intermediates are
thought to react in such arrangement where the RhC bond is
not conjugated to the CO or the NO bond (Figure 3a, out-of-
plane conformation),12d,15a,35 α-cyanocarbenes such as the ones
formed in our system are forced to stay in-plane, thus leading to
a more electrodeficient reactive carbene (Figure 3b). Sterically,
the small and in-plane nitrile functionality leads to a less
encumbered metal−carbene compared with other electron-
withdrawing groups. These properties of diacceptor cyanocar-
benes suggest that such intermediates possess a particular
electrophilicity, permitting less nucleophilic π systems such as
allenes to react. It is noteworthy that such an increase in
reactivity for systems forced to stay in-plane was recently
reported with the use of cyclic α-diazocarbonyl compounds.36
Moreover, from all diacceptor diazo reagents evaluated to date
1
was detected by H NMR of the crude mixtures. Moreover, as
previously observed with α-cyano diazophosphonate 3, the
Rh2(S-IBAZ)4-catalyzed reaction generally proved to be slightly
less efficient in terms of yield, presumably because of a lower
reactivity of the corresponding metal−carbene.
CONCLUSION
In summary, we have developed a highly stereoselective Rh(II)-
catalyzed cyclopropanation of alkenes, alkynes, and allenes with
■
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Table 5. Scope of the Stereoselective Alkylidenecyclopropanation Using α-Cyano Diazo Ester 29
a
b
a
b
c
entry
R1
R2
product yield for cond A (%)
dr for cond A (E:Z)
yield for cond B (%)
dr for cond B (E:Z)
ee for cond B (%)
1
Ph
H
34
54
55
56
57
58
59
60
61
62
63
93
90
97
68
99
81
96
95
51
57
87
>97:3
>97:3
>97:3
>97:3
>97:3
>97:3
>97:3
>97:3
82:18
>97:3
>97:3
92
82
76
74
44
86
80
48
>97:3
>97:3
>97:3
>97:3
>97:3
93:7
95
95
96
96
97
>90
82
90
n.d.
96
90
2
4-Me-C6H4
4-Cl-C6H4
4-MeO-C6H4
2−Br-C6H4
CH2Ph
H
3
H
4
H
5
H
6
H
7
CH2-NPhth
N-phthaloyl
CO2Et
H
>97:3
93:7
8
H
d
d
9
H
29
80:20
>97:3
>97:3
10
Ph
Me
43
11
SiMe3
Me
83
a
b
c
Isolated yield of combined diastereomers. Determined by 1H NMR analysis of the crude mixture. Determined by SFC or GC analysis on chiral
d
stationary phase (ee of E product). Yield of pure E diastereomer.
Notes
diacceptor diazo compounds. By employing the phosphonate
moiety as an effective trans-directing group, the first catalytic
asymmetric method for the synthesis of diacceptor cyclo-
propylphosphonates is reported through the use of α-cyano
diazophosphonate 3 and catalyst Rh2(S-IBAZ)4, under mild
reaction conditions. The reaction was shown to be also efficient
using an isosteric substrate, α-cyano diazophosphonate 29,
leading to the formation of the corresponding cyclopropanes
and cyclopropenes in high yields and stereoselectivities.
Moreover, the particular electrophilicity of cyanocarbene
intermediates permitted the use of allenes as substrates, leading
to the development of the first catalytic asymmetric
alkylidenecyclopropanation reaction using diacceptor diazo
compounds. All the methods reported here employ practical
procedures, avoiding syringe-pump techniques and using
minimal amounts of reagents and catalysts, at 0 °C or room
temperature. Cognizant of the array of existing synthetic
applications of diacceptor cyclopropanes,12−14 cyclopropyl-
phosphonates,2−4 or ACPs,26−30 this work contributes to
access a variety of new and useful enantioenriched cyclo-
propane-based building blocks for the stereoselective synthesis
of complex molecules.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work has been supported by the Natural Science and
Engineering Research Council of Canada (NSERC), the
Canada Research Chair Program, the Canada Foundation for
Innovation, the Centre in Green Chemistry and Catalysis
(CGCC), and the Universite
Francine Belanger-Gariepy and CYLView for X-ray analysis, as
́ ́
de Montreal. We also thank
́
́
well as Christophe Camy and Alexandra Furtos for SFC
analysis. The authors are grateful to Dr. James J. Mousseau for
useful discussions on the manuscript. V.N.G.L. is grateful to
NSERC (PGS D) and Universite
fellowships. D.F. is grateful to NSERC (PGS M) and Universite
de Montreal for postgraduate fellowships. S.A. is grateful to
́ ́
de Montreal for postgraduate
́
́
NSERC (PGS D) for a postgraduate fellowship.
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ASSOCIATED CONTENT
■
S
* Supporting Information
Experimental procedures, compound characterization data, and
NMR spectra for new compounds. This material is available
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AUTHOR INFORMATION
■
Corresponding Author
andre.charette@umontreal.ca
Present Address
†Leibniz University of Hannover, Institute of Organic
Chemistry, Schneiderberg 1, 30167 Hannover, Germany.
Author Contributions
‡These authors contributed equally.
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