Rhodium-Catalyzed Oxidative Benzannulation of N-Pivaloylanilines with Internal Alkynes through Dual C?H Bond Activation: Synthesis of Highly Substituted Naphthalenes

Article abstract of DOI:10.1002/asia.201601131

An efficient method was developed for the synthesis of highly substituted naphthalenes through rhodium-catalyzed oxidative benzannulation of N-pivaloylanilines with internal alkynes. The benzannulation reaction proceeded smoothly through dual C?H bond act

Full text of DOI:10.1002/asia.201601131

CHEMISTRY
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Accepted Article
Title: Rhodium-catalyzed Oxidative Benzannulation of N-Pivaloylanilines with Inter-
nal Alkynes via Dual C-H Bond Activation: Synthesis of Highly Substituted
Naphthalenes
Authors: Xuan Zhang; Xiaoqiang Yu; Yoshinori Yamamoto; Abdulrahman I. Alman-
sour; Natarajan Arumugam; Raju Suresh Kumar; Ming Bao
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Chemistry - An Asian Journal
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Rhodium-catalyzed Oxidative Benzannulation of N-
Pivaloylanilines with Internal Alkynes via Dual C–H Bond
Activation: Synthesis of Highly Substituted Naphthalenes
Xuan Zhang[a], Xiaoqiang Yu*[a], Yoshinori Yamamoto[a,b], Abdulrahman I. Almansour[c], Natarajan
Arumugam[c], Raju Suresh Kumar[c], and Ming Bao*[a]
aState Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116023, China
bWPI-AIMR (WPI-Advanced Institute for Materials Research), Tohoku University, Sendai 980-8577, Japan
cDepartment of Chemistry, College of Sciences, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia
Abstract: An efficient method was developed for the synthesis of
highly substituted naphthalenes through rhodium-catalyzed oxidative
Results and Discussion
benzannulation of N-pivaloylanilines with internal alkynes. The
benzannulation reaction proceeded smoothly via dual C–H bond
In the initial study, the reactions of N-phenylacetamide (1a) and
N-phenylpivalamide (2a) were performed in the presence of
[Cp*RhCl2]2 as a precatalyst and Cu(OAc)2 as an oxidant in tert-
amyl alcohol (tAmOH) at 110 °C for 12 h to investigate the effect
of the steric hindrance of the directing group on the reaction
activation to produce the corresponding highly substituted
naphthalene products in satisfactory to good yields.
regioselectivity (Scheme 1). The benzannulation product 4aa
was obtained in 22% yield along with an indole derivative 4aa' in
Introduction
8% yield from the reaction of 1a with 1,2-diphenylethyne
(3a).These results indicated that the benzannulation reaction
could proceed in the presence of a neutral rhodium(III) catalyst.
The subsequent investigation showed that the undesired indole
forming reaction could be completely inhibited by installing a
sterically hindered tert-butyl into the N-acyl group. The
benzannulation product 5aa was obtained in 24% yield as the
sole product from the reaction of 2a with 3a. This result
motivated us to optimize the reaction conditions for
benzannulation using the neutral rhodium(III) catalyst and
sterically hindered pivaloylamino group as the directing group.
The transition-metal-catalyzed direct functionalization of C–H
bonds recently emerged as an extremely powerful tool for the
synthesis of complex organic molecules.1 To control site
selectivity in molecules that contain diverse C–H bonds, this
method required appropriate directing groups such as
heterocycles,2 aminocarbonyl groups,3 and acylamino groups4
linked on the substrates. Among the directing groups employed,
acylamino groups are frequently utilized because they can be
easily installed into the substrates and converted to other
functional groups.5 For example, the acylamino groups linked on
aromatic rings were successfully used as the directing groups
for new carbon–carbon (including Caryl–Calkenyl6, Caryl–Caryl7, Caryl
–
Scheme 1.Effect of Steric Hindrance of Directing Group on Reaction
Calkyl8, and Caryl–Ccarbonyl9) and carbon–hetero atom (including
Caryl–N10, Caryl–O11, Caryl–B12, Caryl–Cl13, Caryl–Br14, and Caryl–I15)
bond formation as well as for the carbocycle and heterocycle
construction16-18. It was demonstrated that highly functionalized
indoles can be efficiently synthesized through direct C–H bond
functionalization in the presence of a cationic rhodium(III)
catalyst using acetylamino group as the directing group (Eq.
1)17a,17c,17e. In the course of our recent studies on the transition-
metal-catalyzed direct functionalization of C–H bonds, the
regioselectivity in the reaction of N-aryl amides with internal
alkynes is found to be easily turned by using a neutral
rhodium(III) catalyst and a sterically hindered directing group
(Eq.2). The results are reported in the current work.
Regioselectivity.
The benzannulation reaction of 2a with 3a was selected as a
model to optimize the reaction conditions. Results are shown in
Table 1. The use of RhCl3 and RhCl(PPh3)3 as rhodium
precatalysts instead of [Cp*RhCl2]2 led to no reaction (entry 1 vs.
entries 2 and 3). The solvents were then screened using polar
[tAmOH, acetone, 1,4-dioxane, and N,N-dimethyl formamide
(DMF)] and nonpolar [toluene and 1,2-dichloroethane (DCE)]
solvents (entries 1 and 4–8). DMF proved to be the best solvent
among the solvents examined (entry 8, 58% yield).19 The
oxidants were finally screened using [Cp*RhCl2]2 as
a
precatalyst and DMF as a solvent. Cu(OAc)2 proved to be the
best oxidant among the tested oxidants Cu(OAc)2, Cu(OTf)2,
Ag2CO3, and AgOAc (entry 8 vs.entries 9–11). The yield of
benzannulation product 5aa was found to increase with
increased [Cp*RhCl2]2 loading (entry 12, 81%). Therefore, the
subsequent benzannulation reactions of N-pivaloylanilines 2a–
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2p with internal alkynes 3a–3q were performed in the presence
of [Cp*RhCl2]2 as a precatalyst and Cu(OAc)2 as an oxidant in
DMF at 110 °C for 12 h.
aryl- and alkyl-substituted internal alkynes as starting materials
in the presence of palladium catalyst.16
Table 2.Substrate Scope of Internal Alkynesa
Table 1. Reaction Condition Screeninga
Entry
1
2
3
4
5
6
7
8
9
10
11
12d
Catalyst
[Cp*RhCl2]2
RhCl3
Oxidant
Solvent
Yield (%)b
Entry
1
2
3
4
5
6
7
8
Internal Alkyne 3
R1 = R2 = Ph
Product 5
5aa
5ab
5ac
5ad
5ae
5af
5ag
5ah
5ai
5aj
5ak
5al
5am
5an
5ao
5ap
5aq
Yield (%)b
81
Cu(OAc)2•H2O
Cu(OAc)2•H2O
Cu(OAc)2•H2O
Cu(OAc)2•H2O
Cu(OAc)2•H2O
Cu(OAc)2•H2O
Cu(OAc)2•H2O
Cu(OAc)2•H2O
Cu(OTf)2
tAmOH
tAmOH
tAmOH
Toluene
DCE
24
3a
3b
3c
3d
3e
3f
3g
3h
3i
NRc
NRc
NRc
23
R1 = R2 = 4-FC6H4
R1 = R2 = 4-ClC6H4
R1 = R2 = 4-BrC6H4
R1 = R2 = 3-ClC6H4
R1 = R2 = 3-BrC6H4
R1 = R2 = 4-CF3C6H4
R1 = R2 = 4-MeC6H4
R1 = R2 = 3-MeC6H4
R1 = R2 = 2-MeC6H4
R1 = R2 = 4-MeOC6H4
R1 = R2 = 3-MeOC6H4
63
76
81
77
75
70
67
RhCl(PPh3)3
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
Acetone
1,4-dioxane
DMF
DMF
DMF
40
18
58
NRc
NRc
3
9
67
Ag2CO3
AgOAc
Cu(OAc)2•H2O
10
11
12
13
14
15
16
17
3j
3k
3l
NRc
60
DMF
DMF
81
67
aReaction conditions: 2a (0.25 mmol, 44.3 mg), 3a (0.5 mmol, 89.1 mg),
catalyst (2.5 mol%), oxidant (0.5 mmol, 2 equiv) in solvent (2.0 mL) at 110 °C
for 12 h under N2 atmosphere. bIsolated yield. cNo reaction was observed; the
starting materials were recovered. d5 mol% of [Cp*RhCl2]2 was used.
R1 = R2 = 3,5-Me2C6H3 3m
62
R1 = R2 = 2-thienyl
R1 = Ph; R2 = Me
R1 = Ph; R2 = Et
R1 = Ph; R2 = nPr
3n
3o
3p
3q
29d
57
64
60
aReaction conditions: 2a (0.25 mmol, 44.3 mg), 3 (0.5 mmol, 2 equiv),
[Cp*RhCl2]2 (5 mol%, 7.8 mg), Cu(OAc)2·H2O (0.50 mmol, 99.8 mg) in DMF
(2.0 mL) at 110 °C for 12 h under N2 atmosphere. bIsolated yield. cNo reaction
was observed, and the starting materials were recovered. dThe starting
material 2a was recovered in 62% yield.
The reactions of 2a with various internal alkynes 3a–3q were
conducted under optimum conditions to explore the scope and
limitation of the alkyne substrate, and the results are
summarized in Table 2. The reactions of 2a with diarylalkynes
3b–3f bearing electron-withdrawing groups (F, Cl, and Br) on
para- or meta-positions of benzene rings proceeded smoothly to
provide the corresponding benzannulation products 5ab–5af in
moderate to good yields (entries 2–6, 63%–81% yields). The
A
series of N-pivaloylanilines were then examined with
diphenylacetylene (3a) under the optimized reaction conditions
to explore the scope and limitation of the N-pivaloylaniline
substrate. The results are shown in Table 2. N-(o-
tolyl)pivalamide (2b) and N-(m-tolyl)pivalamide (2c) presented
different reactivity in the benzannulation reaction to give the
corresponding products 5ba and 5ca in 50% and 79% yields,
respectively (entries 1 and 2). These results indicated that the
reactivity of the N-pivaloylaniline substrate is significantly
influenced by the steric effect of the substituent linked on the
benzene ring. Surprisingly, when methyl (Me) or normal butyl
(nBu) were substituted at the para-positions of N-pivaloylaniline
substrates, the desired benzannulation reaction could not take
place. However, the hydroarylation reaction of diphenylacetylene
occurred to furnish byproducts 6a–6c (entries 3–5), which was
considered to be produced from the steric hindrance of para-
substituents Me and nBu. Similarly, the reaction of the N-
pivaloylaniline substrate 2g that contains an ortho-methoxy
group gives the benzannulation product 5ga in a relatively low
yield (60%) as the reaction of 2b (entry 6). Good yields were
observed in the reactions of N-pivaloylaniline substrates 2h and
2i, even when the methoxy group was linked on the para-
position (entries 7 and 8). N-Pivaloylaniline substrates 2j, 2k,
and 2l, which bear a chloro atom on the ortho-, meta-, or para-
positions, showed low reactivities in this type of benzannulation
reaction to afford the corresponding products 5ja–5la in low
yields (entries 9–11, 25%–42%). Low yields were also observed
in the reactions of N-pivaloylaniline substrates 2m, 2n, 2o, and
2l bearing electron-withdrawing groups (Br, CO2Et, COMe, and
desired benzannulation product 5ag was isolated in
a
satisfactory yield even when the diarylalkyne substrate 3g
bearing a strong electron-withdrawing group (CF3) on para-
positions of benzene rings (entry 7, 70% yield). The
benzannulation products 5ah, 5ai, and 5ak–5am were obtained
in moderate yields (60%–67%) from the reactions of 2a with
diarylalkynes 3h, 3i, and 3k–3m bearing electron-donating
groups (Me and MeO) on para- or meta-positions of benzene
rings (entries 8, 9, and 11–13). These abovementioned results
indicated that the electronic property of the substituent linked on
the benzene ring did not influence the reactivity of diarylalkyne.
No reaction was observed when the diarylalkyne substrate, 1,2-
di-o-tolylethyne (3j), was examined (entry 10). The non-reactivity
of 3j was considered to be due to the steric hindrance of the
ortho-methyl substituent. The heterocycle-containing alkyne
substrate, 1,2-di(thiophen-2-yl)ethyne (3n), was then tested, and
the corresponding benzannulation product 5an was isolated in
29% yield (entry 14). Surprisingly, when the unsymmetrical
alkynes, 1-phenyl-1-propyne (3o), 1-phenyl-1-butyne (3p), and
1-phenyl-1-pentyne (3q), were finally examined under optimum
conditions, the benzannulation products 5ao–5aq were
selectively obtained in moderate yields (57%–64%), and the
generation of regioisomer was not observed at all. It was
reported that no reaction was observed when this type of
benzannulation was examined using N-acetylanilines and mono
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CN) on meta-positions (entries 12–15, 24%–41%).These
abovementioned results indicated that the electronic property of
the substituents strongly influenced the reactivities of N-
pivaloylaniline substrates. All new products were identified
through their NMR and HRMS data, as well as IR spectra.
Product 5ao was further identified by determining its X-ray
structure.
10
11
12
2k
2l
5ka
5la
41
42
41
Table 3.Substrate Scope of N-pivaloylanilinesa
2m
5ma
13
14
2n
2o
5na
5oa
39g
35h
Yield
Entry
1
N-pivaloylaniline2
Product 5
(%)b
2b
5ba
5ca
5da
5ea
50
2
3
4
2c
2d
2e
79
0c
15
2p
5pa
24i
aReaction conditions: 2 (0.25 mmol), 3a (0.5 mmol, 89.1 mg), [Cp*RhCl2]2 (5
mol%, 7.8 mg), Cu(OAc)2·H2O (0.5 mmol, 99.8 mg) in DMF (2.0 mL) at 110 °C
for 12 h under N2 atmosphere. bIsolated yield. cBy-product 6a was separated
in 20% yield, and the starting material 2d was recovered in 63% yield. dBy-
product 6b was separated in 30% yield, and the starting material 2e was
recovered in 56% yield. eBy-product 6c was separated in 39% yield, and the
f
starting material 2f was recovered in 49% yield. The starting material 2j was
0d
recovered in 70% yield. gThe starting material 2n was recovered in 55% yield.
hThe starting material 2o was recovered in 60% yield. iThe starting material 2p
was recovered in 70% yield.
5
6
7
8
9
2f
2g
2h
2i
5fa
5ga
5ha
5ia
0e
60
85
88
25f
To gain insight into the mechanism of this type of benzanulation
reaction, a deuterium labeling experiment was conducted to
investigate whether the reaction proceeded via the C–H bond
activation pathway (Scheme 2).
A significant amount of
deuterium-labeled 2a-d2 was observed when the N-
pivaloylaniline substrate 2a was treated without alkyne substrate
under optimized reaction conditions in the presence of D2O. This
observation reveals that the target reactions indeed proceeded
via the C–H bond activation pathway. Further study on the
deuterium kinetic isotope effect (DKIE) by conducting an
intermolecular competition reaction between 2a and 2a-d5
demonstrated that the cleavage of the C–H bond in 2a is
involved in the rate-determining step (Scheme 3).
2j
5ja
Scheme 2. H–D Exchange Experiment on Amide Substrate 2a in the
Presence of D2O.
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Scheme 3. Competition Experiments between 2a and 2a-d5.
On the basis of our experimental outcomes and previous
reports18, a plausible catalytic cycle is proposed to account for
the present catalytic benzannulation reaction (Scheme 4). The
catalytic cycle starts from Cp*Rh(OAc)2, which is generated in
situ from the ligand exchange reaction between [Cp*RhCl2]2 and
Cu(OAc)2. The coordination of the oxygen atom of 2a to rhodium
catalyst species and subsequent ortho C–H bond activation
would generate a six-membered rhodacyclic intermediate A with
the liberation of an acetic acid molecule. The insertion of 3o into
the Rh–C bond would regioselectively occur to produce
intermediate B; the regioselectivity might be due to the different
electron densities and steric effects of alkyne substituents (Me
and Ph)20. The intermediate B would subsequently undergo a
second C–H bond activation to afford intermediate C. A second
insertion of alkyne 3o into the Rh–C bond in the intermediate C
would also regioselectively occur to produce intermediate D,
which would subsequently undergo reductive elimination to
generate a highly substituted naphthalene product 5ao and a
Rh(Ι) species. The Rh(Ι) species would then be re-oxidized to
active catalytic species Cp*Rh(OAc)2 by Cu(OAc)2. The
formation of intermediate C' is considered to be inhibited by the
steric hindrance of the tert-butyl group. Consequently, the
formation of the benzoindole product was inhibited.
The intermediate E derived from N-pivaloylaniline substrate 2d
could not proceed cyclorhodation to produce intermediate F,
which was considered to be due to the strong steric hindrance
between Me and Cp* groups. The protonation reaction of
intermediate E with HOAc generated in situ would take place to
provide by-product 6a. For the case of the N-pivaloylaniline
substrate 2i, the rhodacyclic intermediate H would be generated
due to the weak steric hindrance caused in intermediate G;
thereby the desired benzannulation product 5ia could be
obtained in a good yield.
Conclusions
In summary, the regioselectivity in the reaction of N-aryl
amides with internal alkynes was successfully controlled by
using a neutral rhodium(III) catalyst and a sterically hindered
directing group. The rhodium-catalyzed regioselective oxidative
benzannulation reaction proceeded smoothly via a dual C–H
bond cleavage under mild conditions with affordable and simple
starting materials to produce highly-substituted naphthalenes in
moderate-to-good yields. This new protocol shows good
functional group tolerance and broad substrate scope.
Experimental Section
1.1. General information
All reactions were carried out under a nitrogen atmosphere unless
otherwise noted. Solvents were purified by standard techniques without
Scheme 4. Proposed Reaction Mechanism.
1
special instructions. H and 13C NMR spectra were recorded on a Bruker
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27.7; IR (KBr) υ (cm-1) 3306, 2967, 1647, 1601, 1536, 1513, 1478, 1412,
1314, 1233, 1170, 1035, 828; HRMS (ESI) Calcd for C12H17NO2Na
230.1157 [M+Na]+, found 230.1166.
Avance II-400 spectrometer (400 MHz for 1H, 100 MHz for 13C); CDCl3
and TMS were used as a solvent and an internal standard, respectively.
The chemical shifts are reported in ppm downfield (δ) from TMS, the
coupling constants J are given in Hz. The peak patterns are indicated as
follows: s, singlet; d, doublet; t, triplet; m, multiplet; q, quartet. IR spectra
were recorded on a NEXUS FT-IR spectrometer. High resolution mass
spectra were recorded on a GC-TOF mass spectrometry. TLC was
carried out on SiO2 (silica gel 60 F254, Merck), and the spots were located
with UV light, iodoplatinate reagent or 1% aqueous KMnO4. Flash
chromatography was carried out on silica gel (SiO2 60, 200-300 meth).
Melting points were determined using a micro-melting point apparatus
N-(2-chlorophenyl)pivalamide (2j)28. White solid (0.88 g, 83% yield);
mp: 75–76 °C. 1H NMR (400 MHz, CDCl3) δ 8.42 (d, J = 8.4 Hz, 1H),
8.02 (bs, 1H), 7.36 (d, J = 8.0 Hz, 1H), 7. 27 (dd, J = 8.0, 7.6 Hz, 1H),
7.03 (dd, J = 7.6, 7.6 Hz, 1H), 1.35 (s, 9H).
N-(3-chlorophenyl)pivalamide (2k)26. White solid (0.90 g, 85% yield);
1
mp: 124–125 °C. H NMR (400 MHz, CDCl3) δ 7.68 (s, 1H), 7.36 (d, J =
8.0 Hz, 2H), 7.23 (dd, J = 8.0, 8.0 Hz, 1H), 7.27 (dd, J = 8.0, 7.6 Hz, 1H),
7.07 (d, J = 8.0 Hz, 1H), 1.31 (s, 9H).
21
22
and are uncorrected. [Cp*RhCl2]2 and RhCl(PPh3)3 were prepared
from RhCl3•xH2O following a literature procedure. Unless otherwise noted
below, all other compounds have been reported in the literature or are
commercially available without any further purification. The starting
materials 2a–2p,23 and 3b–3n24 were prepared according to the known
procedure.
N-(4-chlorophenyl)pivalamide (2l)29. White solid (0.90 g, 85% yield);
1
mp: 152–153 °C. H NMR (400 MHz, CDCl3) δ 7.48 (d, J = 8.8 Hz, 2H),
7.33 (bs, 1H), 7. 27 (d, J = 8.4 Hz, 2H), 1.31 (s, 9H).
N-(3-bromophenyl)pivalamide (2m)27. White solid (1.08 g, 84% yield);
mp: 137–138 °C. 1H NMR (400 MHz, CDCl3) δ 7.81 (dd, J = 2.0, 1.6 Hz,
1H), 7.42 (d, J = 8.0 Hz, 1H), 7.36 (bs, 1H), 7.22 (d, J = 8.0 Hz, 1H), 7.16
(dd, J = 8.0, 8.0 Hz, 1H), 1.31 (s, 9H).
1.2. Characterization of starting materials 2a–2p
N-pivaloylaniline (2a)25. White solid (3.3 g, 93% yield); mp: 132–133 °C.
1H NMR (400 MHz, CDCl3) δ 7.53 (d, J = 7.6 Hz, 2H), 7.36 (bs, 1H), 7.
31 (dd, J = 8.0, 7.6 Hz, 2H), 7.10 (dd, J = 7.6, 7.2 Hz, 1H), 1.32 (s, 9H).
Ethyl 3-pivalamidobenzoate (2n)26. White solid (1.01 g, 81% yield); mp:
59–60 °C. 1H NMR (400 MHz, CDCl3) δ 8.01 (s, 1H), 7.95 (d, J = 8.0 Hz,
1H), 7.77 (d, J = 8.0 Hz, 1H), 7.55 (bs, 1H), 7.39 (dd, J = 8.0, 8.0 Hz, 1H),
4.37 (q, J = 7.2 Hz, 2H), 1.39 (t, J = 7.2 Hz, 3H), 1.33 (s, 9H).
N-(o-tolyl)pivalamide (2b)26. White solid (0.86 g, 90% yield); mp: 110–
112 °C. 1H NMR (400 MHz, CDCl3) δ 7.86 (d, J = 8.0 Hz, 1H), 7.23–7.17
(m, 3H), 7.06 (dd, J = 7.6, 7.2 Hz, 1H), 2.26 (s, 3H), 1.34 (s, 9H).
N-(3-acetylphenyl)pivalamide (2o)29. White solid (0.88 g, 80% yield);
N-(m-tolyl)pivalamide (2c)27. White solid (0.87 g, 91% yield); mp: 124–
125 °C. 1H NMR (400 MHz, CDCl3) δ 7.43 (s, 1H), 7.29–7.27 (m, 2H), 7.
20 (dd, J = 7.6, 7.6 Hz, 1H), 6.92 (d, J = 7.2 Hz, 1H), 2.33 (s, 3H), 1.31 (s,
9H).
1
mp: 124–126 °C. H NMR (400 MHz, CDCl3) δ 8.05 (s, 1H), 7.90 (d, J =
7.6 Hz, 1H), 7.69 (d, J = 7.6 Hz, 1H), 7.48 (bs, 1H), 7.43 (dd, J = 8.0, 7.6
Hz, 1H), 2.62 (s, 3H), 1.34 (s, 9H).
N-(3-cyanophenyl)pivalamide (2p). White solid (0.84 g, 83% yield); mp:
91–92 °C. 1H NMR (400 MHz, CDCl3) δ 7.98 (s, 1H), 7.74 (d, J = 8.0 Hz,
1H), 7.57 (bs, 1H), 7.43–7.36 (m, 2H), 1.33 (s, 9H); 13C NMR (CDCl3,
100 MHz) δ 177.2, 139.1, 129.9, 127.7, 124.4, 123.3, 118.7, 113.0, 39.9,
27.6; IR (KBr) υ (cm-1) 3356, 2969, 2231, 1665, 1587, 1535, 1480, 1423,
1167, 791, 682; HRMS (ESI) Calcd for C12H14N2ONa 225.1004 [M+Na]+,
found 225.1001.
N-(p-tolyl)pivalamide (2d)26. White solid (0.87 g, 91% yield); mp: 119–
1
120 °C. H NMR (400 MHz, CDCl3) δ 7.40 (d, J = 8.0 Hz, 2H), 7.29 (bs,
1H), 7.11 (d, J = 8.0 Hz, 2H), 2.31 (s, 3H), 1.30 (s, 9H).
N-(3,4-dimethylphenyl)pivalamide (2e)25. Light yellow solid (0.92 g,
1
90% yield); mp: 129–130 °C. H NMR (400 MHz, CDCl3) δ 7.36 (s, 1H),
7.24–7.21 (m, 2H), 7.06 (d, J = 8.0 Hz, 1H), 2.24 (s, 3H), 2.21 (s, 3H),
1.3. General Procedure for Synthesis of highly substituted
naphthalenes 5 from N-pivaloylanilines 2a–2p and internal alkynes
3a–3q
1.30 (s, 9H).
N-(4-butylphenyl)pivalamide (2f). White solid (1.04 g, 89% yield); mp:
72–74 °C. 1H NMR (400 MHz, CDCl3) δ 7.43 (d, J = 6.8 Hz, 2H), 7.32 (bs,
1H), 7.12 (d, J = 7.6 Hz, 2H), 2.57 (t, J = 7.6 Hz, 2H), 1.60–1.53 (m, 2H),
1.36–1.30 (m, 11H), 0.91 (t, J = 7.6 Hz, 3H); 13C NMR (CDCl3, 100 MHz)
δ 176.6, 139.0, 135.7, 128.9, 120.1, 39.7, 35.2, 33.8, 27.8, 22.4, 14.1; IR
(KBr) υ (cm-1) 3315, 2956, 2928, 1653, 1597, 1519, 1408, 1317, 825;
HRMS (ESI) Calcd for C15H23NONa 256.1677 [M+Na]+, found 256.1679.
A mixture of N-pivaloylaniline (2, 0.25 mmol, 1 equiv.), internal alkyne (3,
0.50 mmol, 2.0 equiv.), [Cp*RhCl2]2 (3.9 mg, 0.00625 mmol, 2.5 mol%),
and Cu(OAc)2•H2O (99.8 mg, 0.50 mmol, 2.0 equiv.) were charged in a
Schlenk tube equipped with a stir bar. Dry DMF (2.0 mL) was added and
the mixture was stirred at 110 °C for 12 h under N2 atmosphere. The
mixture was then washed with H2O (3 × 20 mL) and extracted with CHCl3
(3 × 20 mL). The combined organic phase were dried with Na2SO4. All
volatiles were evaporated under reduced pressure. The purification was
performed by flash column chromatography on silica gel (eluent:
petroleum ether : ethyl acetate = 10 : 1) to afford the corresponding
highly substituted naphthalene product.
N-(2-methoxyphenyl)pivalamide (2g)27. White solid (0.93 g, 90% yield);
mp: 39–40 °C. 1H NMR (400 MHz, CDCl3) δ 8.41 (d, J = 8.0 Hz, 1H),
8.13 (bs, 1H), 7.02 (dd, J = 8.0, 8.0 Hz, 1H), 6. 96 (dd, J = 8.0, 8.0 Hz,
1H), 6.87 (d, J = 8.0 Hz, 1H), 3.90 (s, 3H), 1.32 (s, 9H).
N-(3-methoxyphenyl)pivalamide (2h)27. White solid (0.93 g, 90% yield);
mp: 130–131 °C. 1H NMR (400 MHz, CDCl3) δ 7.39 (s, 1H), 7.35 (bs, 1H),
7.20 (dd, J = 8.0, 8.0 Hz, 1H), 6.94 (d, J = 7.2 Hz, 1H), 6.66 (d, J = 8.4
Hz, 1H), 3.80 (s, 3H), 1.32 (s, 9H).
1.4. Characterization of highly substituted naphthalenes 4, 5 and by-
products 6
N-(5,6,7,8-tetraphenylnaphthalen-1-yl)acetamide (4aa)16.
N-(4-methoxyphenyl)pivalamide (2i). White solid (0.95 g, 92% yield);
White solid (27.0 mg, 22% yield); mp: 146–148 °C. 1H NMR (400 MHz,
1
mp: 102–103 °C. H NMR (400 MHz, CDCl3) δ 7.41 (d, J = 8.8 Hz, 2H),
7.36 (bs, 1H), 6.82 (d, J = 8.8 Hz, 2H), 3.77 (s, 3H), 1.28 (s, 9H); 13
C
CDCl3) δ 7.95 (d, J = 5.9Hz, 1H), 7.50 (d, J = 6.8Hz, 1H), 7.40 (dd, J =
NMR (CDCl3, 100 MHz) δ 176.6, 156.4, 131.2, 122.1, 114.1, 55.6, 39.5,
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133.9, 133.7, 133.30, 133.27, 133.2, 133.13, 133.10, 133.03, 132.96,
132.93, 132.88, 132.8, 131.1, 131.0, 130.84, 130.78, 129.72, 129.68,
129.3, 129.2, 129.1, 128.9, 128.8, 128.7, 128.6, 128.4, 128.3, 127.7,
127.5, 126.8, 126.5, 126.3, 126.1, 125.9, 39.4, 27.1; IR (KBr) υ (cm-1)
3441, 3318, 2963, 1656, 1594, 1564, 1479, 1407, 1373, 1091, 1077, 908,
884, 778, 758, 732, 699; HRMS (ESI) m/z Calcd for C39H29NONaCl4
690.0901 [M+Na]+, found 690.0915.
6.2, 6.7 Hz, 1H), 7.26–7.16 (m, 10H), 6.99 (bs, 1H), 6.85–6.73 (m, 10H),
1.40(s, 3H).
1-(2,3-diphenyl-1H-indol-1-yl)ethanone (4aa’)17a
.
White solid (6.3 mg, 8% yield); mp: 139–141 °C. 1H NMR (400 MHz,
CDCl3) δ 8.44 (d, J = 8.4 Hz, 1H), 7.54 (d, J = 7.8 Hz, 1H), 7.41–7.37 (m,
1H), 7.35–7.19(m, 11H), 1.99 (s, 3H).
N-(5,6,7,8-tetraphenylnaphthalen-1-yl)pivalamide (5aa).
N-(5,6,7,8-tetrakis(3-bromophenyl)naphthalen-1-yl)pivalamide (5af).
1
White solid (107.7 mg, 81% yield); mp: 159–160 °C. H NMR (400 MHz,
1
White solid (158.9 mg, 75% yield); mp: 117–119 °C. H NMR (400 MHz,
CDCl3) δ 7.88 (d, J = 7.6 Hz, 1H), 7.49 (d, J = 8.2 Hz, 1H), 7.40 (dd, J =
8.2, 7.6 Hz, 1H), 7.24–7.14 (m, 11H), 6.82–6.74 (m, 8H), 6.64–6.62 (m,
2H), 0.80 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 177.0, 142.3, 141.3,
140.5, 140.3, 139.9, 139.5, 139.0, 134.4, 134.2, 133.6, 131.3, 131.1,
128.5, 127.7, 127.2, 126.7, 126.5, 125.8, 125.6, 125.5, 125.3, 124.9,
39.4, 27.0; IR (KBr) υ (cm-1) 3425, 3337, 3050, 3024, 1670, 1601, 1493,
1475, 1441, 1382, 1157, 910, 778, 736, 730, 698; HRMS (ESI) m/z Calcd
for C39H34NO 532.2640 [M+H]+, found 532.2645.
CDCl3) δ 7.82 (dd, J = 4.4, 4.3 Hz, 1H), 7.48 (d, J = 4.6 Hz, 2H), 7.40–
7.31 (m, 4H), 7.20–6.49 (m, 13H), 0.87 (s, 9H); 13C NMR (100 MHz,
CDCl3) δ 177.1, 143.8, 141.4, 141.3, 141.1, 139.5, 138.5, 137.2, 134.1,
133.9, 133.81, 133.78, 133.6, 133.5, 130.51, 130.47, 130.3, 129.90,
129.85, 129.7, 129.5, 129.3, 129.2, 129.1, 128.8, 128.7, 128.5, 128.4,
126.8, 126.4, 125.9, 125.8, 122.8, 122.7, 122.18, 122.15, 122.10, 122.05,
122.01, 121.96, 121.38, 121.35, 121.2, 121.1, 120.99, 120.96, 39.3,
27.0; IR (KBr) υ (cm-1) 3440, 3321, 3060, 2958, 2925, 2868, 1661, 1592,
1559, 1477, 1403, 1374, 1215, 1161, 1070, 996, 884, 817, 804, 756, 721,
695; HRMS (ESI) m/z Calcd for C39H29NONaBr4 865.8880 [M+Na]+,
found 865.8918.
N-(5,6,7,8-tetrakis(4-fluorophenyl)naphthalen-1-yl)pivalamide (5ab).
White solid (95.1 mg, 63% yield); mp: 182–184 °C. 1H NMR (400 MHz,
CDCl3) δ 7.82 (d, J = 6.2 Hz, 1H), 7.48–7.41(m, 2H), 7.14–7.05(m, 5H),
6.96–6.89 (m, 4H), 6.68–6.65 (m, 2H), 6.59–6.56 (m, 6H), 0.87 (s, 9H);
13C NMR (100 MHz, CDCl3) δ176.9, 161.8 (d, 1JC–F = 246.7 Hz), 161.6 (d,
1JC–F = 244.7 Hz), 160.7 (d, 1JC–F = 243.9 Hz), 160.6 (d, 1JC–F = 244.2 Hz),
140.4, 138.9, 138.2, 137.80 (d, 4JC-F = 3.0 Hz) , 135.97 (d, 4JC-F = 2.9 Hz),
135.81 (4JC-F = 2.6 Hz), 135.29 (4JC-F = 3.0 Hz), 134.1 (2JC-F = 20.5 Hz),
132.53 (3JC-F = 7.8 Hz), 132.23 (3JC-F = 7.6 Hz), 126.12 (2JC-F = 19.1 Hz),
N-(5,6,7,8-tetrakis(4-(trifluoromethyl)phenyl)naphthalen-1-
yl)pivalamide (5ag).
1
White solid (140.6 mg, 70% yield); mp: 271–273 °C. H NMR (400 MHz,
CDCl3) δ 7.73 (d, J = 7.2 Hz, 1H), 7.54–7.44 (m, 6H), 7.29 (d, J = 7.9 Hz,
4H), 7.16–7.10 (m, 4H), 6.87 (d, J = 7.8 Hz, 2H), 6.83 (s, 1H), 6.75 (d, J
= 7.8 Hz, 2H), 0.81 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 177.3, 145.5,
143.1, 142.7, 139.4, 138.9, 137.2, 134.4, 134.0, 133.7, 131.4, 131.3,
131.1, 131.0, 129.9–127.9 (m), 127.5, 127.2, 126.8, 126.1, 125.5, 125.2,
125.1, 125.1, 124.3 (q, JC–F = 3.0 Hz), 124.0 (q, JC–F = 3.1 Hz), 122.7,
122.5, 39.3, 26.9; IR (KBr) υ (cm-1) 3357, 2955, 2918, 2849, 1654, 1616,
1457, 1324, 1165, 1122, 1105, 1065, 1019, 846, 756; HRMS (ESI) m/z
Calcd for C43H29NONaF12 826.1955 [M+Na]+, found 826.1960.
2
125.7, 125.66, 125.64, 125.56, 115.35(d, JC–F = 21.0 Hz), 114.84 (d,
2JC–F = 21.1 Hz), 114.1, 114.0, 113.9, 113.8, 39.2, 26.9; IR (KBr) υ (cm-1)
3444, 3321, 2956, 2917, 2848, 1659, 1604, 1509, 1478, 1380, 1224,
1157, 1093, 1015, 909, 830, 816, 777, 758, 734; HRMS (ESI) m/z Calcd
for C39H29NONaF4 626.2083 [M+Na]+, found 626.2088.
N-(5,6,7,8-tetrakis(4-chlorophenyl)naphthalen-1-yl)pivalamide (5ac).
1
White solid (127.2 mg, 76% yield); mp: 268–270 °C. H NMR (400 MHz,
N-(5,6,7,8-tetra-p-tolylnaphthalen-1-yl)pivalamide (5ah).
CDCl3) δ 7.76 (dd, J = 5.0, 3.7 Hz, 1H), 7.44–7.43 (m, 2H), 7.26–7.18 (m,
4H), 7.07 (dd, J = 10.0, 8.4 Hz, 4H), 6.92 (s, 1H), 6.89–6.86 (m, 4H), 6.64
(d, J = 8.4 Hz, 2H), 6.55 (d, J = 8.4 Hz, 2H), 0.88 (s, 9H); 13C NMR (100
MHz, CDCl3) δ 177.0, 140.1, 139.7, 138.7, 138.2, 138.0, 137.7, 137.6,
134.1, 134.0, 133.5, 133.4, 133.0, 132.3, 132.2, 132.0, 131.9, 128.6,
128.2, 127.4, 127.3, 126.5, 126.33, 126.31, 125.7, 39.3, 26.9; IR (KBr) υ
(cm-1) 3439, 3326, 2960, 2921, 2865, 1653, 1492, 1395, 1378, 1092,
1015, 908, 837, 771, 758, 734; HRMS (ESI) m/z Calcd for
C39H29NONaCl4 690.0901 [M+Na]+, found 690.0890.
White solid (98.5 mg, 67% yield); mp: 194–196 °C. 1H NMR (400 MHz,
CDCl3) δ 7.88 (d, J = 6.7 Hz, 1H), 7.44 (d, J = 8.4 Hz, 1H), 7.34 (dd, J =
8.2, 7.8 Hz, 1H), 7.06–6.96 (m, 9H), 6.62–6.59 (m, 6H), 6.49 (d, J = 7.9
Hz, 2H), 2.29 (s, 3H), 2.26 (s, 3H), 2.09 (s, 3H), 2.07 (s, 3H), 0.81 (s,
9H); 13C NMR (100 MHz, CDCl3) δ 177.0, 141.5, 139.4, 139.20, 139.17,
137.7, 137.4, 137.1, 136.6, 135.8, 134.44, 134.37, 134.30, 134.25, 133.5,
131.2, 131.1, 131.0, 129.1, 128.3, 127.3, 127.2, 125.43, 125.38, 124.2,
39.3, 26.9, 21.4, 21.3, 21.2; IR (KBr) υ (cm-1) 3421, 3022, 2956, 2923,
2868, 1670, 1510, 1466, 1378, 1157, 1110, 1021, 817, 756, 744; HRMS
(ESI) m/z Calcd for C43H41NONa 610.3086 [M+Na]+, found 610.3094.
N-(5,6,7,8-tetrakis(4-bromophenyl)naphthalen-1-yl)pivalamide (5ad).
1
White solid (163.1 mg, 77% yield); mp: 272–274 °C. H NMR (400 MHz,
N-(5,6,7,8-tetra-m-tolylnaphthalen-1-yl)pivalamide (5ai).
CDCl3) δ 7.75 (dd, J = 3.6, 3.6Hz, 1H), 7.43 (d, J = 3.6Hz, 2H), 7.39 (d, J
= 6.4Hz, 2H), 7.34 (d, J = 6.8Hz, 2H), 7.06–6.98 (m, 8H), 6.89 (s, 1H),
6.59 (d, J = 6.4Hz, 2H), 6.49 (d, J = 6.4Hz, 2H), 0.88 (s, 9H); 13C NMR
(100 MHz, CDCl3) δ 177.1, 140.6, 139.5, 138.7, 138.6, 138.5, 138.2,
137.4, 134.1, 134.0, 133.6, 132.6, 132.4, 132.3, 131.5, 131.2, 130.4,
130.3, 126.6, 126.5, 126.3, 125.8, 121.6, 121.3, 120.4, 120.2, 39.3, 26.9;
IR (KBr) υ (cm-1) 3438, 3329, 2956, 2924, 2854, 1654, 1489, 1391, 1101,
1071, 1011, 908, 827, 774, 764, 732; HRMS (ESI) m/z Calcd for
C39H29NONaBr4 865.8880 [M+Na]+, found 865.8846.
White solid (98.5 mg, 67% yield); mp: 92–94 °C. 1H NMR (400 MHz,
CDCl3) δ 7.93 (d, J = 7.5 Hz, 1H), 7.49 (d, J = 8.4 Hz, 1H), 7.41 (s, 1H),
7.38 (dd, J = 8.1, 8.0 Hz, 1H), 7.10–6.92 (m, 8H), 6.72–6.38 (m, 8H),
2.25–2.14 (m, 6H), 2.01–1.94 (m, 6H), 0.80 (s, 9H); 13C NMR (100 MHz,
CDCl3) δ 176.9, 142.2, 142.1, 141.5, 141.4, 140.3, 140.2, 139.9, 139.4,
139.33, 139.29, 139.0, 137.9, 137.8, 136.87, 136.85, 136.8, 135.7, 135.6,
135.49, 135.45, 135.4, 134.19, 134.15, 134.1, 133.5, 132.2, 132.1, 131.9,
128.4, 128.3, 128.24, 128.17, 128.0, 127.81, 127.75, 127.4, 127.3, 127.2,
126.3, 126.2, 126.1, 126.0, 125.7, 125.5, 125.4, 125.0, 124.1, 39.4, 26.9,
21.5, 21.2, 21.1; IR (KBr) υ (cm-1) 3420, 3345, 3015, 2957, 2921, 2867,
1672, 1603, 1584, 1509, 1487, 1378, 1157, 1090, 779, 755, 733, 700;
HRMS (ESI) m/z Calcd for C43H41NONa 610.3086 [M+Na]+, found
610.3088.
N-(5,6,7,8-tetrakis(3-chlorophenyl)naphthalen-1-yl)pivalamide (5ae).
1
White solid (135.6 mg, 81% yield); mp: 120–122 °C. H NMR (400 MHz,
CDCl3) δ 7.81 (dd, J = 3.9, 3.8 Hz, 1H), 7.48–7.46 (m, 2H), 7.22–7.02 (m,
9H), 6.89–6.47 (m, 8H), 0.87 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 177.2,
143.6, 141.3, 141.2 140.9, 139.6, 138.7, 137.3, 134.8, 134.6, 134.0,
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N-(5,6,7,8-tetrakis(4-methoxyphenyl)naphthalen-1-yl)pivalamide
(5ak).
129.0, 127.6, 127.4, 126.3, 126.1, 126.0, 125.5, 124.1, 39.5, 27.7, 22.2,
17.9; IR (KBr) υ (cm-1) 3284, 2954, 2923, 2852, 1645, 1508, 1457, 1377,
1206, 748, 699; HRMS (ESI) m/z Calcd for C29H29NONa 430.2147
[M+Na]+, found 430.2139.
White solid (97.8 mg, 60% yield); mp: 102–104 °C. 1H NMR (400 MHz,
CDCl3) δ 7.92 (d, J = 7.3 Hz, 1H), 7.47 (d, J = 8.4 Hz, 1H), 7.36 (dd, J =
8.2, 7.9 Hz, 1H), 7.32 (s, 1H), 7.08–7.03 (m, 4H), 6.78–6.72 (m, 4H),
6.62 (d, J = 8.6 Hz, 2H), 6.51 (d, J = 8.6 Hz, 2H), 6.40–6.37 (m, 4H), 3.78
(s, 3H), 3.75 (s, 3H), 3.63 (s, 3H), 3.61 (s, 3H), 0.84 (s, 9H); 13C NMR
(100 MHz, CDCl3) δ 176.8, 158.5, 158.0, 156.9, 141.5, 139.2, 134.5,
134.3, 134.1, 133.5, 133.2, 132.9, 132.4, 132.3, 132.12, 132.05, 132.0,
125.4, 125.2, 123.9, 113.9, 113.1, 112.1, 55.4, 55.2, 55.0, 54.9, 39.3,
27.0; IR (KBr) υ (cm-1) 3416, 2956, 2835, 1675, 1609, 1511, 1463, 1285,
1244, 1176, 1107, 1033, 830, 801, 755, 733; HRMS (ESI) m/z Calcd for
C43H41NO5Na 674.2882 [M+Na]+, found 674.2897.
N-(5,8-diethyl-6,7-diphenylnaphthalen-1-yl)pivalamide (5ap).
White solid (69.7 mg, 64% yield); mp: 91–93 °C. 1H NMR (400 MHz,
CDCl3) δ 8.14 (d, J = 7.0 Hz, 1H), 7.78 (s, 1H), 7.54–7.53 (m, 2H), 7.12–
7.04 (m, 6H), 6.98–6.93 (m, 4H), 3.01 (q, J = 7.3 Hz, 2H), 2.83 (q, J = 7.4
Hz, 2H), 1.35 (s, 9H), 1.14 (t, J = 7.4 Hz, 3H), 1.06 (t, J = 7.4 Hz, 3H); 13
C
NMR (100 MHz, CDCl3) δ177.3, 141.7, 141.5, 141.4, 139.4, 136.6, 134.5,
133.73, 133.71, 130.2, 130.1, 128.4, 128.1, 127.28, 127.25, 126.0, 125.3,
125.0, 39.5, 27.6, 25.6, 24.1, 16.9, 15.6; IR (KBr) υ (cm-1) 3302, 2965,
2931, 2872, 1651, 1602, 1496, 1442, 1366, 1238, 1185, 1167, 909, 760,
739, 700; HRMS (ESI) m/z Calcd for C31H33NONa 458.2460 [M+Na]+,
found 458.2465.
N-(5,6,7,8-tetrakis(3-methoxyphenyl)naphthalen-1-yl)pivalamide (5al).
1
White solid (109.2 mg, 67% yield); mp: 101–103 °C. H NMR (400 MHz,
CDCl3) δ 7.85 (d, J = 7.5 Hz, 1H), 7.57–7.54 (m, 1H), 7.41 (dd, J = 8.1,
7.9 Hz, 1H), 7.32 (s, 1H), 7.19–7.10 (m, 2H), 6.86–6.69 (m, 8H), 6.41–
6.18 (m, 6H), 3.69–3.66 (m, 3H), 3.62–3.59 (m, 3H), 3.50–3.46 (m, 6H),
0.84 (s, 9H); 13C NMR (400 MHz, CDCl3) δ 177.0, 159.51, 159.45,
158.94, 158.89, 158.12, 158.06, 143.4, 141.6, 141.5, 141.1, 140.7,
140.61, 140.57, 139.2, 138.3, 134.2, 134.0, 133.5, 129.5, 129.4, 128.63,
128.57, 127.6, 125.8, 125.6, 125.5, 125.1, 124.0, 123.9, 123.3, 116.5,
116.4, 116.1, 114.14, 114.08, 112.7, 112.0, 55.31, 55.26, 55.19, 55.15,
39.4, 27.0; IR (KBr) υ (cm-1) 3420, 3000, 2956, 2834, 1672, 1600, 1578,
1486, 1465, 1427, 1376, 1284, 1246, 1214, 1159, 1045, 877, 756, 740,
697; HRMS (ESI) m/z Calcd for C43H41NO5Na 674.2882 [M+Na]+, found
674.2870.
N-(6,7-diphenyl-5,8-dipropylnaphthalen-1-yl)pivalamide (5aq).
White solid (69.5 mg, 60% yield); mp: 139–141 °C. 1H NMR (400 MHz,
CDCl3) δ 8.08 (d, J = 8.3 Hz, 1H), 7.74 (s, 1H), 7.55 (d, J = 7.0 Hz, 1H),
7.50 (dd, J = 8.1, 7.5 Hz, 1H), 7.11–7.03 (m, 6H), 6.97–6.93 (m, 4H),
2.95 (t, J = 8.0 Hz, 2H), 2.75 (t, J = 8.1 Hz, 2H), 1.61–1.55 (m, 2H), 1.46–
1.41 (m, 2H), 1.35 (s, 9H), 0.82 (t, J = 7.2 Hz, 3H), 0.64 (t, J = 7.2 Hz,
3H); 13C NMR (100 MHz, CDCl3) δ 177.3, 142.0, 141.9, 141.7, 139.6,
135.4, 134.02, 133.98, 133.5, 130.5, 130.3, 128.4, 127.3, 126.0, 125.3,
124.8, 39.7, 34.6, 33.3, 27.8, 25.5, 24.7, 14.9, 14.4; IR (KBr) υ (cm-1)
3299, 2959, 2929, 2870, 1652, 1601, 1496, 1466, 1442, 1367, 1239,
1255, 1183, 1167, 909, 753, 733, 700; HRMS (ESI) m/z Calcd for
C33H37NONa 486.2773 [M+Na]+, found 486.2764.
N-(5,6,7,8-tetrakis(3,5-dimethylphenyl)naphthalen-1-yl)pivalamide
(5am).
N-(2-methyl-5,6,7,8-tetraphenylnaphthalen-1-yl)pivalamide
(5ba).
White solid (68.2 mg, 50% yield); mp: 230–232 °C. 1H NMR (400 MHz,
CDCl3) δ 7.51 (d, J = 8.7 Hz, 1H), 7.30–7.08 (m, 11H), 6.78–6.67 (m,
10H), 6.47 (s, 1H), 2.26 (s, 3H), 0.84 (s, 9H); 13C NMR (100 MHz, CDCl3)
δ 176.2, 143.8, 141.5, 140.59, 140.56, 139.9, 139.1, 138.4, 135.9, 134.8,
132.9, 131.7, 131.4, 131.3, 131.1, 130.7, 129.7, 129.6, 129.2, 129.1,
128.4, 128.1, 127.6, 127.0, 126.54, 126.49, 126.4, 125.4, 125.1, 39.2,
27.1, 19.5; IR (KBr) υ (cm-1) 3435, 3341, 2956, 2924, 2854, 1649, 1492,
1459, 1441, 1383, 1157, 1071, 1027, 829, 759, 737, 699; HRMS (ESI)
m/z Calcd for C40H35NONa 568.2616 [M+Na]+, found 568.2635.
White solid (99.8 mg, 62% yield); mp: 206–208 °C. 1H NMR (400 MHz,
CDCl3) δ 7.99 (d, J = 6.9 Hz, 1H), 7.62 (s, 1H), 7.48 (d, J = 7.6 Hz, 1H),
7.35 (dd, J = 8.2, 7.8 Hz, 1H), 6.80–6.77 (m, 5H), 6.72 (s, 1H), 6.39 (d, J
= 11.5 Hz, 4H), 6.25 (s, 2H), 2.19 (s, 6H), 2.13 (s, 6H), 1.95 (s, 6H), 1.94
(s, 6H), 0.80 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 176.8, 141.9, 141.6,
140.1, 139.8, 139.1, 138.9, 137.5, 136.4, 135.01, 134.96, 134.9, 133.9,
133.4, 129.0, 128.42, 128.35, 127.84, 127.75, 126.6, 126.5, 126.2, 125.1,
124.4, 123.1, 39.3, 26.7, 21.3, 21.2, 21.0; IR (KBr) υ (cm-1) 3415, 3002,
2956, 2917, 2864, 1673, 1601, 1513, 1479, 1388, 1375, 1355, 1260,
1205, 1157, 907, 843, 773, 755, 735, 704; HRMS (ESI) m/z Calcd for
C47H49NONa 666.3712 [M+Na]+, found 666.3729.
N-(3-methyl-5,6,7,8-tetraphenylnaphthalen-1-yl)pivalamide
(5ca).
1
White solid (107.8 mg, 79% yield); mp: 244–246 °C. H NMR (400 MHz,
CDCl3) δ 7.81 (s, 1H), 7.25–7.13 (m, 12H), 6.81–6.73 (m, 8H), 6.63–6.61
(m, 2H), 2.38 (s, 3H), 0.80 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 176.9,
142.2, 140.6, 140.4, 140.0, 139.0, 138.8, 135.6, 134.24, 134.17, 133.3,
131.3, 131.1, 128.3, 127.6, 127.1, 126.5, 126.4, 125.34, 125.29, 125.14,
125.06, 124.6, 124.5, 123.6, 39.3, 26.9, 21.7; IR (KBr) υ (cm-1) 3421,
3343, 2955, 2923, 1669, 1507, 1494, 1457, 1441, 1400, 1165, 1071,
1027, 858, 757, 735, 698; HRMS (ESI) m/z Calcd for C40H35NONa
568.2616 [M+Na]+, found 568.2615.
N-(5,6,7,8-tetra(thiophen-2-yl)naphthalen-1-yl)pivalamide (5an).
Yellowish solid (40.3 mg, 29% yield); mp: 150–152 °C. 1H NMR (400
MHz, CDCl3) δ 7.97 (d, J = 7.5 Hz, 1H), 7.71 (d, J = 8.4 Hz, 1H), 7.59 (s,
1H), 7.48 (dd, J = 8.1, 8.0 Hz, 1H), 7.34–7.31 (m, 2H), 7.05–6.91 (m, 6H),
6.66–6.63 (m, 2H), 6.54 (d, J = 3.0 Hz, 1H), 6.48 (d, J = 3.0 Hz, 1H), 0.97
(s, 9H); 13C NMR (100 MHz, CDCl3) δ 177.2, 142.6, 140.63, 140.56,
139.7, 136.4, 135.3, 135.1, 134.5, 133.6, 130.1, 129.9, 129.7, 129.4,
129.30, 129.26, 129.0, 127.8, 127.4, 126.99, 126.96, 126.7, 126.5, 126.1,
125.9, 125.6, 125.4, 124.3, 120.1, 39.6, 27.2; IR (KBr) υ (cm-1) 3416,
3343, 2960, 2926, 2868, 1669, 1501, 1473, 1368, 1224, 1158, 909, 850,
834, 756, 732, 693; HRMS (ESI) m/z Calcd for C31H25NONaS4 578.0717
[M+Na]+, found 578.0729.
N-(2-methoxy-5,6,7,8-tetraphenylnaphthalen-1-yl)pivalamide (5ga).
White solid (84.3 mg, 60% yield); mp: 259–261 °C. 1H NMR (400 MHz,
CDCl3) δ 7.61 (d, J = 9.4 Hz, 1H), 7.23–7.00 (m, 10H), 6.77–6.69 (m,
10H), 6.53 (s, 1H), 6.36 (s, 1H), 3.87 (s, 3H), 0.86 (s, 9H); 13C NMR (100
MHz, CDCl3) δ 177.3, 154.0, 143.3, 141.9, 140.6, 140.5, 139.9, 138.9,
137.2, 134.7, 131.6, 131.3, 131.2, 131.0, 130.9, 130.0, 129.8, 128.8,
128.5, 127.8, 127.6, 127.4, 126.5, 126.3, 126.1, 125.3, 125.0, 120.1,
113.4, 56.7, 39.0, 27.2; IR (KBr) υ (cm-1) 3445, 3328, 3056, 3023, 2958,
2925, 2868, 1673, 1602, 1505, 1482, 1441, 1353, 1280, 1118, 756, 698;
N-(5,8-dimethyl-6,7-diphenylnaphthalen-1-yl)pivalamide (5ao).
White solid (58.1 mg, 57% yield); mp: 198–200 °C. 1H NMR (400 MHz,
CDCl3) δ 8.04 (d, J = 8.4 Hz, 1H), 7.73 (s, 1H), 7.69 (d, J = 7.4 Hz, 1H),
7.52 (dd, J = 8.1, 7.8 Hz, 1H), 7.14–7.04 (m, 6H), 6.96–6.93 (m, 4H),
2.52 (s, 3H), 2.42 (s, 3H), 1.34 (s, 9H); 13C NMR (100 MHz, CDCl3) δ
176.8, 142.0, 141.9, 141.7, 139.6, 134.4, 134.2, 130.5, 130.2, 129.1,
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HRMS (ESI) m/z Calcd for C40H35NO2Na 584.2565 [M+Na]+, found
758, 732, 696; HRMS (ESI) m/z Calcd for C39H32NONaCl 588.2070
[M+Na]+, found 588.2056.
584.2569.
N-(3-methoxy-5,6,7,8-tetraphenylnaphthalen-1-yl)pivalamide (5ha).
N-(3-bromo-5,6,7,8-tetraphenylnaphthalen-1-yl)pivalamide (5ma).
White solid (62.6 mg, 41% yield); mp: 252–254 °C. 1H NMR (400 MHz,
CDCl3) δ 8.21 (d, J = 1.7 Hz, 1H), 7.60 (d, J = 1.8 Hz, 1H), 7.36 (s, 1H),
7.24–7.12 (m, 10H), 6.81–6.71 (m, 8H), 6.62–6.60 (m, 2H), 0.78 (s, 9H);
13C NMR (100 MHz, CDCl3) δ 177.0, 141.6, 141.4, 140.1, 140.0, 139.9,
139.1, 138.8, 135.04, 134.96, 134.5, 131.2, 131.14, 131.10, 130.9, 128.6,
127.8, 127.6, 127.0, 126.7, 126.6, 126.4, 125.6, 125.4, 123.6, 120.0,
39.5, 26.9; IR (KBr) υ (cm-1) 3416, 3056, 3023, 2962, 1671, 1590, 1492,
1441, 1370, 1345, 1156, 1073, 1027, 911, 889, 859, 753, 733, 697;
HRMS (ESI) m/z Calcd for C39H32NONaBr 632.1565 and 634.1545
[M+Na]+, found 632.1574 and 634.1562.
1
White solid (119.4 mg, 85% yield); mp: 184–186 °C. H NMR (400 MHz,
CDCl3) δ 7.86 (d, J = 2.4 Hz, 1H), 7.35(s, 1H), 7.22–7.12 (m, 10H), 6.82–
6.74 (m, 9H), 6.63–6.61 (m, 2H), 3.70 (s, 3H), 0.78 (s, 9H); 13C NMR
(100 MHz, CDCl3) δ 176.9, 157.0, 141.9, 140.6, 140.4, 140.1, 139.3,
139.0, 138.3, 135.2, 134.3, 131.4, 131.24, 131.19, 131.0, 128.5, 127.7,
127.3, 126.6, 126.5, 125.4, 125.1, 120.5, 114.7, 105.0, 55.3, 39.4, 27.0;
IR (KBr) υ (cm-1) 3420, 3056, 3022, 2960, 1674, 1618, 1513, 1493, 1442,
1401, 1356, 1261, 1204, 1178, 1166, 1146, 1069, 910, 756, 734, 699;
HRMS (ESI) m/z Calcd for C40H35NO2Na 584.2565 [M+Na]+, found
584.2587.
Ethyl 5,6,7,8-tetraphenyl-4-pivalamido-2-naphthoate (5na).
N-(4-methoxy-5,6,7,8-tetraphenylnaphthalen-1-yl)pivalamide (5ia).
White solid (58.9 mg, 39% yield); mp: 138–140 °C. 1H NMR (400 MHz,
CDCl3) δ 8.41 (s, 1H), 8.28 (s, 1H), 7.22–7.15 (m, 11H), 6.82–6.73 (m,
8H), 6.63–6.62 (m, 2H), 4.32 (q, J = 7.2 Hz, 2H), 1.32 (t, J = 7.2 Hz, 3H),
0.81 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 177.1, 166.5, 143.5, 141.7,
141.1, 140.1, 139.94, 139.86, 139.0, 134.6, 134.0, 133.7, 131.3, 131.0,
128.5, 128.2, 127.9, 127.8, 127.7, 127.4, 127.0, 126.8, 126.6, 125.7,
125.5, 124.0, 61.2, 39.4, 27.0, 14.4; IR (KBr) υ (cm-1) 3283, 3057, 3024,
2960, 2928, 2869, 1719, 1649, 1493, 1463, 1441, 1403, 1273, 1235,
1173, 1102, 1028, 910, 769, 732, 697; HRMS (ESI) m/z Calcd for
C42H37NO3Na 626.2671 [M+Na]+, found 626.2662.
1
White solid (123.6 mg, 88% yield); mp: 100–102 °C. H NMR (400 MHz,
CDCl3) δ 7.57 (d, J = 8.3 Hz, 1H), 7.13 (s, 5H), 7.06–6.98 (m, 5H), 6.87
(s, 1H), 6.83 (d, J = 8.4 Hz, 1H), 6.76 (s, 6H), 6.65 (d, J = 5.9 Hz, 2H),
6.58–6.57 (m, 2H), 3.34 (s, 3H), 0.81 (s, 9H); 13C NMR (100 MHz, CDCl3)
δ 177.1, 155.6, 144.0, 142.6, 141.5, 140.39, 140.36, 139.8, 137.3, 134.4,
131.4, 131.2, 130.9, 129.6, 128.7, 128.3, 127.0, 126.8, 126.4, 126.33,
126.28, 125.5, 125.1, 124.9, 107.0, 56.0, 39.2, 27.0; IR (KBr) υ (cm-1)
3437, 3327, 3056, 3022, 2956, 2926, 2868, 1663, 1601, 1573, 1493,
1460, 1441, 1366, 1260, 1129, 1071, 757, 736, 697; HRMS (ESI) m/z
Calcd for C40H35NO2Na 584.2565 [M+Na]+, found 584.2545.
N-(3-acetyl-5,6,7,8-tetraphenylnaphthalen-1-yl)pivalamide (5oa).
Yellowish solid (50.2 mg, 35% yield); mp: 176–178 °C. 1H NMR (400
MHz, CDCl3) δ 8.40 (s, 1H), 8.12 (s, 1H), 7.28–7.16 (m, 11H), 6.83–6.74
(m, 8H), 6.63–6.62 (m, 2H), 2.49 (s, 3H), 0.81 (s, 9H); 13C NMR (100
MHz, CDCl3) δ 197.9, 177.2, 143.7, 141.5, 141.2, 140.0, 139.8, 139.0,
134.6, 134.4, 134.1, 133.7, 131.2, 131.02, 130.97, 128.5, 127.9, 127.8,
127.5, 127.1, 127.0, 126.8, 126.6, 125.7, 125.5, 122.6, 39.4, 27.0, 26.7;
IR (KBr) υ (cm-1) 3420, 3056, 3024, 2958, 2925, 2865, 1684, 1601, 1493,
1456, 1441, 1402, 1274, 1220, 1171, 910, 734, 698; HRMS (ESI) m/z
Calcd for C41H35NO2Na 596.2565 [M+Na]+, found 596.2565.
N-(2-chloro-5,6,7,8-tetraphenylnaphthalen-1-yl)pivalamide (5ja).
White solid (35.4 mg, 25% yield); mp: 244–246 °C. 1H NMR (400 MHz,
CDCl3) δ 7.55 (d, J = 9.1 Hz, 1H), 7.44 (d, J = 9.2 Hz, 1H), 7.30–7.26 (m,
3H), 7.20–6.98 (m, 8H), 6.89–6.71 (m, 9H), 6.69 (s, 1H), 6.64 (d, J = 6.8
Hz, 1H), 6.45 (d, J = 7.4 Hz, 1H), 0.87 (s, 9H); 13C NMR (100 MHz,
CDCl3) δ 176.8, 142.9, 142.4, 140.2, 140.0, 139.6, 139.3, 139.2, 135.5,
133.1, 132.7, 131.6, 131.1, 130.9, 130.8, 130.7, 130.42, 130.36, 129.8,
128.4, 128.2, 127.8, 127.74, 127.66, 127.1, 126.81, 126.75, 126.6, 126.5,
126.4, 125.6, 125.3, 39.3, 27.1; IR (KBr) υ (cm-1) 3441, 3322, 3057, 3023,
2958, 2925, 2869, 1672, 1599, 1491, 1442, 1214, 1160, 1072, 1023, 926,
793, 756, 737, 698; HRMS (ESI) m/z Calcd for C39H32NONaCl 588.2070
[M+Na]+, found 588.2086.
N-(3-cyano-5,6,7,8-tetraphenylnaphthalen-1-yl)pivalamide (5pa).
1
Yellow solid (33.4 mg, 24% yield); mp: 110–112 °C. H NMR (400 MHz,
CDCl3) δ 8.27 (s, 1H), 7.83 (s, 1H), 7.43 (s, 1H), 7.25–7.20 (m, 8H), 7.12
(d, J = 6.4 Hz, 2H), 6.84–6.80 (m, 6H), 6.73–6.71 (m, 2H), 6.61–6.59 (m,
2H), 0.79 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 177.2, 144.4, 140.85,
140.77, 140.3, 139.6, 139.5, 138.4, 135.1, 134.6, 133.6, 131.13, 131.08,
130.9, 130.8, 130.6, 128.8, 128.1, 127.9, 127.4, 126.9, 126.7, 126.4,
125.9, 125.7, 123.2, 119.1, 109.4, 39.6, 26.9; IR (KBr) υ (cm-1) 3416,
3057, 3024, 2958, 2925, 2227, 1684, 1493, 1441, 1396, 1158, 1071,
1027, 735, 698; HRMS (ESI) m/z Calcd for C40H32N2ONa 579.2412
[M+Na]+, found 579.2410.
N-(3-chloro-5,6,7,8-tetraphenylnaphthalen-1-yl)pivalamide (5ka).
White solid (58.0 mg, 41% yield); mp: 213–215 °C. 1H NMR (400 MHz,
CDCl3) δ 8.10 (d, J = 2.0 Hz, 1H), 7.43 (d, J = 2.1 Hz, 1H), 7.38 (s, 1H),
7.24–7.13 (m, 10H), 6.82–6.78 (m, 6H), 6.74–6.72 (m, 2H), 6.62–6.60 (m,
2H), 0.78 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 177.0, 141.6, 141.5,
140.2, 140.1, 140.0, 139.2, 138.9, 135.2, 134.8, 134.5, 131.8, 131.3,
131.2, 131.0, 128.7, 127.9, 127.6, 127.0, 126.8, 126.6, 125.7, 125.4,
123.9, 123.9, 123.7, 123.4, 39.5, 27.0; IR (KBr) υ (cm-1) 3417, 3335,
3057, 3025, 2963, 2928, 2869, 1673, 1598, 1493, 1455, 1441, 1376,
1347, 1245, 1158, 1027, 909, 861, 733, 698; HRMS (ESI) m/z Calcd for
C39H33NOCl 566.2251 [M+H]+, found 566.2300.
(E)-N-(2-(1,2-diphenylvinyl)-4-methylphenyl)pivalamide (6a).
1
Colorless oil (18.5 mg, 20% yield). H NMR (400 MHz, CDCl3) δ 8.12 (d,
J = 8.3 Hz, 1H), 7.41 (bs, 1H), 7.24–7.15 (m, 11H), 7.11 (s, 1H), 6.75 (s,
1H), 2.32 (s, 3H), 0.99 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 176.5,
139.6, 138.8, 137.0, 134.5, 133.6, 133.2, 132.2, 131.6, 129.9, 129.5,
129.3, 128.9, 128.4, 128.3, 127.5, 121.9, 39.7, 27.5, 21.0; IR (neat) υ
(cm-1) 3429, 3055, 3022, 2958, 2925, 2867, 1684, 1588, 1513, 1492,
1445, 1301, 1157, 921, 822, 759, 697; HRMS (ESI) m/z Calcd for
C26H27NONa 392.1990 [M+Na]+, found 392.2005.
N-(4-chloro-5,6,7,8-tetraphenylnaphthalen-1-yl)pivalamide (5la).
White solid (59.4 mg, 42% yield); mp: 205–207 °C. 1H NMR (400 MHz,
CDCl3) δ 7.80 (d, J = 6.4Hz, 1H), 7.51 (d, J = 6.4Hz, 1H), 7.18–7.12 (m,
6H), 7.08–7.03 (m, 5H), 6.81–6.78 (m, 6H), 6.63–6.62 (m, 2H), 6.55 (d, J
= 4.8Hz, 2H), 0.81 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 176.9, 141.6,
141.4, 141.31, 141.25, 140.0, 139.9, 137.8, 134.8, 133.0, 131.6, 131.2,
131.1, 130.8, 129.8, 129.2, 128.5, 127.4, 126.9, 126.6, 126.5, 126.3,
125.4, 124.3, 39.4, 27.0; IR (KBr) υ (cm-1) 3426, 3332, 3056, 3021, 2956,
2924, 2853, 1669, 1600, 1492, 1458, 1442, 1363, 1326, 1215, 1028, 814,
(E)-N-(2-(1,2-diphenylvinyl)-4,5-dimethylphenyl)pivalamide (6b).
1
Colorless oil (28.8 mg, 30% yield). H NMR (400 MHz, CDCl3) δ 8.06 (s,
1H), 7.38 (bs, 1H), 7.25–7.13 (m, 10H), 7.06 (s, 1H), 6.73 (s, 1H), 2.28 (s,
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3H), 2.23 (s, 3H), 0.99 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 176.5,
139.5, 139.0, 137.2, 137.1, 133.3, 132.3, 132.1, 131.9, 130.0, 129.5,
128.9, 128.4, 128.2, 127.3, 123.0, 39.7, 27.5, 19.9, 19.3; IR (neat) υ (cm-
1) 3429, 3055, 3021, 2960, 2925, 2867, 1684, 1574, 1516, 1491, 1479,
1448, 1400, 1200, 1166, 921, 881, 756, 710, 695; HRMS (ESI) m/z Calcd
for C27H29NONa 406.2147 [M+Na]+, found 406.2156.
[3]
For selected examples, see: (a) Karthikeyan, J.; Cheng, C.-H. Angew.
Chem., Int. Ed. 2011, 50, 9880. (b) Wang, H.; Grohmann, C.; Nimphius,
C.; Glorius, F. J. Am. Chem. Soc. 2012, 134, 19592. (c) Wang, H.;
Beiring, B.; Yu, D.-G.; Collins, K. D.; Glorius, F. Angew. Chem., Int. Ed.
2013, 52, 12430. (d) Zhang, S.-Y.; Li, Q.; He, G.; Nack, W. A.; Chen, G.
J. Am. Chem. Soc. 2015, 137, 531. (e) Zhang, L.-B.; Hao, X.-Q.; Liu, Z.-
J.; Zheng, X.-X.; Zhang, S.-K.; Niu, J.-L.; Song, M.-P. Angew. Chem.,
Int. Ed. 2015, 54, 10012. (f) Hermann, G. N.; Becker, P.; Bolm, C.
Angew. Chem., Int. Ed. 2016, 55, 3781.
(E)-N-(4-butyl-2-(1,2-diphenylvinyl)phenyl)pivalamide (6c).
1
Colorless oil (40.1 mg, 39% yield). H NMR (400 MHz, CDCl3) δ 8.13 (d,
[4]
For selected examples, see: (a) Boele, M. D. K.; Van Strijdonck, G. P.
F.; De Vries, A. H. M.; Kamer, P. C. J.; De Vries, J. G.; Van Leeuwen, P.
W. N. M. J. Am. Chem. Soc. 2002, 124, 1586. (b) Brasche, G.; García-
Fortanet, J.; Buchwald, S. L. Org. Lett. 2008, 10, 2207. (c) Li, C.; Wang,
L.; Li, P.; Zhou, W. Chem. Eur. J. 2011, 17, 10208. (d) Neufeldt, S. R.;
Seigerman, C. K.; Sanford, M. S. Org. Lett. 2013, 15, 2302.(e) Hubrich,
J.; Himmler, T.; Rodefeld, L.; Ackermann, L. Adv. Synth. Catal. 2015,
357, 474.
J = 8.4 Hz, 1H), 7.39 (bs, 1H), 7.23–7.15 (m, 12H), 7.10 (d, J = 2.4 Hz,
1H), 6.76 (s, 1H), 2.58 (t, J = 7.7 Hz, 2H), 1.63–1.56 (m, 2H), 1.40–1.31
(m, 2H), 0.99 (s, 9H), 0.92 (t, J = 7.3 Hz, 3H); 13C NMR (100 MHz, CDCl3)
δ 176.4, 139.7, 138.7, 137.0, 134.4, 133.3, 132.1, 131.0, 130.0, 129.5,
128.9, 128.7, 128.4, 128.3, 127.4, 121.9, 39.7, 35.2, 33.8, 27.5, 22.5,
14.1; IR (neat) υ (cm-1) 3430, 3056, 3022, 2956, 2929, 2869, 1686, 1586,
1513, 1445, 1412, 1300, 1158, 922, 759, 697; HRMS (ESI) m/z Calcd for
C29H33NONa 434.2460 [M+Na]+, found 434.2451.
[5]
[6]
Zhou, J.; Li, B.; Hu, F.; Shi, B.-F. Org. Lett. 2013, 15, 3460.
Selected examples for Caryl–Calkenylbond formation via C–H bond
activation, see: (a) Nishikata, T.; Lipshutz, B. H. Org. Lett. 2010, 12,
1972. (b) Patureau, F. W.; Glorius, F. J. Am. Chem. Soc. 2010, 132,
9982. (c) Ackermann, L.; Wang, L.; Wolfram, R.; Lygin, A. V. Org. Lett.
2012, 14, 728.(d) Manikandan, R.; Jeganmohan, M. Org. Lett. 2014, 16,
912. (e) Hermann, G. N.; Becker, P.; Bolm, C. Angew. Chem., Int. Ed.
2015, 54, 7414. (f) Takahama, Y.; Shibata, Y.; Tanaka, K. Chem. Eur. J.
2015, 21, 9053. (g) Manikandan, R.; Madasamy, P.; Jeganmohan, M.
ACS Catal. 2016, 6, 230.
Acknowledgements
We are grateful to the National Natural Science Foundation of
China [Nos. 21372035, 21573032, and 21361140375 (NSFC-
IUPAC program)] for their financial support. This work was also
supported by the Fundamental Research Funds for the Central
Universities (DUT15LK37). The authors extend their
appreciation to the International Scientific Partnership Program
ISPP at King Saud University for funding this research work
through ISPP#0048.
[7]
Selected examples for Caryl–Carylbond formation via C–H bond activation,
see:(a) Daugulis, O; Zaitsev, V. G. Angew. Chem., Int. Ed. 2005, 44,
4046. (b) Shi, Z.-J; Li, B.; Wan, X.; Cheng, J.; Fang, Z.; Cao, B.; Qin,
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Keywords: Rhodium catalysis • Benzannulation • N-
Pivaloylaniline • Naphthalene
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Xuan Zhang, Xiaoqiang Yu*, Xiujuan
Feng,
Yoshinori
Yamamoto,
Abdulrahman I. Almansour, Natarajan
Arumugam, and Raju Suresh Kumar,
Ming Bao*
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The regioselectivity in the reaction of N-aryl amides with internal alkynes could be
easily turned by using a neutral rhodium(III) catalyst and sterically hindered
directing group to prepare highly substituted naphthalenes.
Rhodium-catalyzed
Oxidative
Benzannulation of N-Pivaloylanilines
with Internal Alkynes via Dual C–H
Bond Activation: Synthesis of Highly
Substituted Naphthalenes
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