Domino [Pd]-Catalysis: Heck followed by decarboxylative Sonogashira couplings under microwave irradiation in aqueous medium

Article abstract of DOI:10.1016/j.jorganchem.2019.03.015

A copper free [Pd]-catalyzed domino intramolecular Heck and intermolecular decarboxylative Sonogashira couplings, for the synthesis of alkyne bearing heterocyclic compounds with a quaternary carbon atom, is described. Notably, this dual bond forming strategy is successful in water solvent, under microwave irradiation. This one-pot operation enabled the formation of a variety of dihydrobenzofurans, indolines and oxindoles, in very good to near quantitative yields. Notably, unlike earlier reports, the present strategy is successful in delivering the products with short alkyl substituents on acetylene carbon, which is first of its kind.

Full text of DOI:10.1016/j.jorganchem.2019.03.015

Accepted Manuscript
Domino [Pd]-Catalysis: Heck followed by decarboxylative Sonagashira couplings
under microwave irradiation in aqueous medium
Karu Ramesh, Gedu Satyanarayana
PII:
S0022-328X(19)30105-6
DOI:
https://doi.org/10.1016/j.jorganchem.2019.03.015
JOM 20743
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 22 January 2019
Revised Date: 15 March 2019
Accepted Date: 16 March 2019
Please cite this article as: K. Ramesh, G. Satyanarayana, Domino [Pd]-Catalysis: Heck followed by
decarboxylative Sonagashira couplings under microwave irradiation in aqueous medium, Journal of
Organometallic Chemistry (2019), doi: https://doi.org/10.1016/j.jorganchem.2019.03.015.
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ACCEPTED MANUSCRIPT
Domino [Pd]-Catalysis: Heck Followed by Decarboxylative Sonagashira
Couplings under Microwave Irradiation in Aqueous Medium
Karu Ramesh and Gedu Satyanarayana*
Department of Chemistry, Indian Institute of Technology Hyderabad, Kandi – 502 285, Sangareddy, Telangana, INDIA
Phone: (040) 2301 6033; Fax: (040) 2301 6003 / 32, E-mail: gvsatya@iith.ac.in
Abstract: A copper free [Pd]-catalyzed domino intramolecular Heck and intermolecular
decarboxylative Sonogashira couplings, for the synthesis of alkyne bearing heterocyclic
compounds with a quaternary carbon atom, is described. Notably, this dual bond forming
strategy is successful in water solvent, under microwave irradiation. This one-pot operation
enabled the formation of a variety of dihydrobenzofurans, indolines and oxindoles, in very good
to near quantitative yields. Notably, unlike earlier reports, the present strategy is successful in
delivering the products with short alkyl substituents on acetylene carbon, which is first of its
kind.
Keywords: Pd-catalysis; Decarboxylation; Aqueous medium; Domino; Microwaves.
Introduction:
In nature, the alkyne moiety is predominant in many products of biological relevance
1
and is also significant in synthetic functional materials. Chemically, the alkyne moiety can be
2
easily converted into different functional groups. Specifically, for the synthesis of internal

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3
alkynes, Sonogashira coupling has been a powerful synthetic method, which almost replaced
4
the existing classical synthetic processes. However, the main constraint of this transformation
is the formation of symmetrical 1,3-diyne byproduct (Glaser product) via homocoupling of
5
terminal acetylenes. Thus noteworthy advancements have been accomplished on this reaction.
6
For example, propiolic acids have been recognized as good alternative source for acetylenes.
probably due to their increased stability and ready availability, compared to that of terminal
alkynes. Significantly, versatility of carboxylic acids is not limited to Sonogashira coupling but
7
also well established in various coupling reactions of transition metal catalysis. Moreover, in
organic synthesis, the design and the development of sustainable domino one-pot synthetic
strategies is vital and desirable along with investigating new methodologies for the construction
of ring systems.
8
9
10
The dihydrobenzofurans, indolines and oxindoles with a quaternary carbon atom at
their 3-position are some of the core structures that constitute many natural and
pharmaceutical products. Hence, many reports have been presented on their synthesis which
1
1
include classical approaches as well as transition metal catalyzed transformations. To the best
of our knowledge, there has been no report for the accomplishment of 3,3’-disubtituted
dihydrocoumarins, indolines and oxindoles using alkyl propiolic acids as Sonogashira coupling
1
2
partners. As a part of our interest on palladium catalyzed domino one-pot processes, we have
described microwave assisted domino one-pot synthesis of 3,3’-disubstituted
dihydrobenzofurans possessing alkyne moiety via intramolecular Heck reaction of ortho-
iodoarylallyl ethers followed by Sonogashira coupling with terminal acetylenes, catalyzed by
1
3
palladium. Inspired by these results, subsequently, it was further applied to the synthesis of
alkyne bearing dihydrobenzofurans, indolines and oxindoles with a quaternary carbon centre, in
1
4
water solvent. Herein, we describe microwave assisted palladium catalyzed one-pot synthesis
of dihydrobenzofurans, indolines and oxindoles from alkyl propiolic acid. The reaction proceeds
through the intramolecular Heck and intermolecular decarboxylative Sonogashira couplings.
Notably, the reaction was feasible in water as the sole solvent, in the presence of quaternary
ammonium salts.

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Result and Discussions
It was envisioned that propiolic acids 2 could serve as good alkyne source for
intermolecular decarboxylative Sonogashira coupling on the bicyclic intermediate B, to furnish
the target heterocyclic products 5/6/7. The bicyclic organo palladium intermediate B could be
resulted from 1/3/4 via intramolecular Heck coupling (Scheme 1).
Scheme 1: Anticipated formation of heterocyclic products.
The optimization study of palladium catalyzed dual coupling process has begun with
ortho-iodophenyl allyl ether 1a and phenylpropiolic acid 2a, particularly, under microwave
irradiation conditions. Accordingly, 1a and 2a in DMF (0.5 mL) were subjected to microwave
irradiation, in the presence of Pd (dba) (1 mol%), base K CO (3 equiv), at 100 °C for 10 min
2
3
2
3
(Table 1, entry 1). This led to formation of product 5aa in 95% yield. As we intend to make our
method environmentally benign, the reaction was explored in water medium. Hence, the
reaction performed between 1a and 2a under the same set of conditions (i.e. Table 1, entry 1),
by replacing DMF with water (Table 1, entry 2). However, the dihydrobenzofuran 5aa was
isolated in poor yield. Increasing the irradiation time to 20 and 30 min, respectively, could not
show much improvement (Table 1, entries 3 & 4). Significantly, when tetrabutylammonium
iodide (TBAI) was used as an additive, the reaction was quite successful and afforded 5aa in
85% yield (Table 1, entry 5). Delightfully, 5aa was isolated in near quantitative yield with
tetrabutylammonium bromide (TBAB) as an additive (Table 1, entry 6). When
benzyltriethylammonium chloride (BTEAC) as an additive, the yield of 5aa was slightly

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decreased (Table 1, entry 7). The yield was moderate, in the presence of base 1,8-
diazabicyclo[5.4.0]undec-7-ene (DBU) (Table 1, entry 8). Reducing the irradiation time to 5 min,
3 4
afforded 5aa in 65% yield (Table 1, entry 9). The catalyst Pd(PPh ) furnished 5aa in 85% yield
(Table 1, entry 10). On the other hand, when the reaction was performed under conventional
heating conditions, in H O and DMF, furnished 5aa as major product along with minor
2
impurities as inseparable mixture (Table 1, entries 11 & 12). Therefore, it was confirmed that
microwave assisting conditions are better than the conventional ones.
a,b,c,d
Table 1. Screening study to the generation of dihydrobenzofuran 5aa from 1a and 2a.
entry
catalyst
additive
(1 equiv)
base
solvent
DMF
temp
time
yield
b
(1 mol%)
(3 equiv)
(°C)
(min)
5aa (%)
1
2
3
4
5
6
7
8
9
Pd (dba)
-
-
K2CO3
100
100
100
100
100
100
100
100
100
100
100
100
10
10
20
30
10
10
10
10
5
(95%)
(15%)
(20%)
(25%)
(85%)
(98%)
(92%)
(40%)
(65%)
(85%)
2
2
3
Pd
(dba)
3
3
3
3
K
2
CO
3
2
H O
Pd (dba)
-
K2CO3
K2CO3
K2CO3
H O
2
2
Pd (dba)
-
H O
2
2
Pd (dba)
TBAI
TBAB
BTEAC
BTEAC
TBAB
TBAB
TBAB
-
H O
2
2
Pd
2
(dba)
3
3
3
3
K
2
CO
3
2
H O
Pd (dba)
K2CO3
DBU
H O
2
2
Pd (dba)
H O
2
2
Pd
2
(dba)
K
2
CO
3
2
H O
1
0
Pd(PPh3)4
Pd (dba)
K2CO3
K2CO3
K2CO3
H O
2
10
60
60
c
1
d
-
1
H O
2
2
3
3
c
2
d
-
1
Pd (dba)
DMF
2
a
Conditions: Reactions were conducted under microwave irradiation (100 °C, 10 minutes, 300 W, closed vessel) using 68.5 mg
(0.25 mmol) of 1-iodo-2-((2-methylallyl)oxy)benzene 1a, 54.7 mg (0.37 mmol) of 3-phenylprop-2-ynoic acid 2a, base (1 mmol, 3
b
c
equiv), Pd-catalyst (1 mol%) and solvent water (0.5 mL) or solvent DMF (0.5 mL). Isolated yields of 5aa. Reactions were
d
performed using conventional heating method. 5aa was obtained as major product along with minor inseparable impurities.

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Since it was clear that entry 6 of Table 1 were best, for the preparation of
dihydrobenzofuran 5aa, next, it was planned to test the reaction with other ortho-iodophenyl
allyl ethers. Thus, ortho-iodophenyl allyl ethers 1b-1h were subjected to microwave irradiation
with phenylpropiolic acid 2a, under standard conditions. Gratifyingly, the reaction was quite
suitable and furnished the corresponding dihydrobenzofurans 5ba-5ha, in excellent yields
(Table 2). Notably, the alkyl-substituted ortho-iodophenyl allyl ethers 1b-1d were smoothly
transformed into dihydrobenzofurans 5ba-5da (Table 2). The protocol was also feasible with
phenyl substituted ortho-iodophenyl allyl ether 1e (5ea, Table 2). To our delight, the reaction
was tolerable to electron deactivating halo-substituents on the aromatic ring of ortho-
iodophenyl allyl ethers 1f-1h (5fa-5ha, Table 2). Furthermore, to elaborate the reaction
feasibility, we have performed a reaction with 1-bromo-2-((2-methylallyl)oxy)benzene 1i and
phenylpropiolic acid 2a, under standard conditions. In this case, the reaction was inferior;
probably due to poor reactivity of bromides when compared to iodides (5ia). While bromo-
substituted ortho-iodophenyl allyl ether 1h (1 equiv) with phenylpropiolic acid 2a (1.5 or 2.0
equiv) under standard conditions, resulted single product 5ha, in which bromo group is intact.
From these observations, it can be rationalized that bromo moiety is unreactive under these
particular conditions. In essence, the bromo-substituted product 5ha, is interesting, as it can
allow the possibility for further elaboration using transition metal catalyzed cross-coupling
reactions.

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a,b,c,d
Table 2: Synthesis of dihydrobenzofurans 5aa-5ia from allyl ethers 1a-1i and phenylpropiolic acid 2a.
H O
2
O
HOOC
R1
O
Me
Pd2(dba)3 (1 mol%)
TBAB (1 equiv)
K2CO3 (3 equiv)
R1
CO2
+
Me
I
1a-1i
2a
MW, 100 C, 10 min
5aa-5ia
O
O
O
Me
Me
Me
Me
Me
5aa (98%)
5ba (92%)
5ca (96%)
O
O
O
Me
Me
Me
F
Me
Me
Me
5da (91%)
5ea (90%)
5fa (95%)
O
O
O
Cl
Br
Me
Me
Me
5ia (0%)d
5ga (94%)
5ha (92%)d (90%)e
a
2 3
Reaction conditions: 1-iodo-2-((2-methylallyl)oxy)benzenes 1a-1i (0.25 mmol), phenylpropiolic acid 2a (0.37 mmol), Pd (dba)
b
(1 mol%), TBAB (1 equiv), K
2
CO
3
(3 equiv), solvent water (0.5 mL), 100 °C, 10 minutes (300 W, closed vessel). Yields in the
c
parenthesis are chromatographically isolated pure products. In the products 5aa-5ia first alphabet refers to the ortho-
d
iodophenyl allyl ethers, and the second alphabet indicates the phenylpropyolic acid. Reaction with 1.5 equiv of phenylpropiolic
e
f
acid 2a. Reaction with 2.0 equiv of phenylpropiolic acid 2a. Reaction with 1-bromo-2-((2-methylallyl)oxy)benzenes 1i instead
of 1a.
Notably, further, the strategy was successfully applied to different 3-alkylpropiolic acids
2b-2d, under established conditions, and the dihydrobenzofurans 5ab-5fd were obtained in
very good yields (Table 3). It is worth noting that none of the previous reports disclosed the
preparation of dihydrobenzofurans with short alkyl-substituents connected to an alkyne carbon
atom. This is due to the fact that short terminal alkylacetylenes are volatile enough and very
difficult to store and handle. Remarkably, the present strategy was found to be superior over
earlier reports and facilitated the synthesis of dihydrobenzofurans 5ab-fd with short alkyl-
substituents on the acetylenic carbon (Table 3). Thus, from these results, it became evident that
simple 3-alkylpropiolic acids are the best alternative alkynyl source over the corresponding
terminal acetylenes.

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a,b,c
Table 3: Synthesis of dihydrobenzofurans 5ab-5fd from allyl ethers 1a-1h and 3-alkylpropiolic acids 2b-2d.
a
Reaction conditions: 1-iodo-2-((2-methylallyl)oxy)benzenes 1a-1h (0.25 mmol), 3-alkylpropiolic acids 2b-2d (0.37 mmol),
b
Pd (dba) (1 mol%), TBAB (1 equiv), K CO (3 equiv), solvent water (0.5 mL), 100 °C, 10 minutes (300 W, closed vessel). Yields in
2
3
2
3
c
the parenthesis are chromatographically isolated pure products. In the products 5ab-5fd first alphabet refers to the ortho-
iodophenyl allyl ethers, and the second alphabet indicates the 3-alkylpropiolic acids.
With the synthesis of dihydrobenzofurans 5aa-5ha and 5ab-5fd (Tables 2 & 3), to
further ascertain the utility of this one-pot green process, it was intended to apply the strategy
for the synthesis of nitrogen heterocyclic products. Therefore, different ortho-iodophenyl
alkyl/benzyl/aryl allyl amines 3a-3d were treated with propiolic acids 2a-2d, under standard
microwave irradiation conditions. Gratifyingly, as expected, the dual C−C bond forming reaction
via a dual coupling sequence was quite smooth and gave the corresponding indolines 6aa-6da,
in very good to excellent yields (Table 4).

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a,b,c
Table 4: Making of indolines 6aa-6da from allyl amines 3a-3d and propiolic aicds 2a-2d.
a
Reaction conditions: 2-iodo-N-alkyl/benzyl/aryl-N-(2-methylallyl)anilines 3a-3d (0.25 mmol), propiolic acids 2a-2d (0.37 mmol)
b
Pd
2
(dba)
3
(1 mol%), TBAB (1 equiv), K
2
CO
3
(3 equiv), solvent water (0.5 mL), 100 °C, 10 minutes (300 W, closed vessel). Yields in
c
the parenthesis are chromatographically isolated pure products. The first alphabet of products 6aa-6da refers to the 2-iodo-N-
alkyl/benzyl/aryl-N-(2-methylallyl)aniline, while, second letter indicates the propiolic acid.
Furthermore, to emphasize the significance of the present method, ortho-iodophenyl
enamides 4a-4c were also reacted with propiolic acids 2a-2d, under standard reaction
conditions. This resulted in the desired oxindoles 7aa-7cd in very good to excellent yields (Table
5), thus, reveals the usefulness of the present strategy for intramolecular Heck and
intermolecular decarboxylative Sonogashira couplings in water as the sole solvent, under
microwave assisted palladium catalysis. Moreover, to the extent of our knowledge, we believe

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this is the first report by making use of propiolic acids as alkynyl source, under decarboxylative
Sonogashira coupling, for the synthesis of dihydrobenzofurans, indolines and oxindoles. It is
noteworthy that all accomplished products with short alkyl substituents on acetyelenic carbon,
is first of its kind.
a,b,c
Table 5: Synthesis of oxindoles 7aa-7cd from alkylmethacrylamides 4a-4c and propiolic acids 2a-2d.
a
Reaction conditions: N-(2-iodophenyl)-N-alkyl/benzylmethacrylamides 4a-4c (0.25 mmol), propiolic aicds 2a-2d (0.37 mmol)
b
Pd
2
(dba)
3
(1 mol%), TBAB (1 equiv), K
2
CO
3
(3 equiv), solvent water (0.5 mL), 100 °C, 10 minutes (300 W, closed vessel). Yields in
c
the parenthesis are chromatographically isolated pure products. In the products 7aa-7cd first alphabet refers to the N-(2-
iodophenyl)-N-methylmethacrylamides, and the second alphabet indicates the propiolic acids.
In addition, to understand reactivity of propioloic acids, control experiment was carried out in
the presence of phenyl propiolic acid 2a and butynoic acid 2b, under standard conditions
(Scheme 2). It is worth noting that phenyl propiolic acid 2a is highly reactive than butynoic acid 2b and

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exclusively afforded the product 5aa. This may be attributed to electron withdrawing nature of phenyl
2
sp carbons and would accelerate the decarboxylation step.
Scheme 2: Control experiments.
The plausible reaction mechanism for the synthesis of 5/6/7 is presented in Scheme 3.
The organo palladium(II) intermediate A can be formed through the oxidative insertion of Pd(0)
2
across the C(sp )-I bond of 1/3/4. Subsequently, bicyclic alkyl-Pd(II) species B would be formed
via intramolecular Heck cyclization of A. Chelation of propiolic acid with palladium(II) of bicyclic
intermediate B, gives C through the removal of KI and KHCO . Decarboxylation of C, furnishes a
3
new Pd(II) species D. Finally, reductive elimination of D, yields the desired heterocyclic products
5/6/7 along with the regeneration of Pd(0) catalyst.

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Scheme 3: Plausible reaction mechanism for the synthesis of heterocycles 5/6/7.
Conclusions
In conclusion, a [Pd]-catalyzed domino one-pot technique was described, for the construction
of alkyne bearing heterocyclic compounds with a quaternary carbon atom. The entire process
involved intramolecular Heck reaction and intermolecular decarboxylative copper free
Sonogashira coupling. Notably, this domino strategy has been successful in the solvent water as
reaction medium, under microwave assisting conditions. Significantly, as far as we know, this is
the initial report on the synthesis of heterocyclic products bearing short alkyl substituents on
the acetylenic carbon atom. This has become possible due to easy handling of short alkyl-
substituted propiolic acids as the Sonogashira coupling partners, as the direct use, handling and
storage of short alkyl substituted acetylenes is difficult.
Experimental
1
General: IR spectra were recorded on a Bruker Tensor 37 (FTIR) spectrophotometer. H NMR
spectra were recorded on Bruker Avance 400 (400 MHz) spectrometer at 295 K in CDCl3;
chemical shifts (δ ppm) and coupling constants (Hz) are reported in standard fashion with
reference to either internal standard tetramethylsilane (TMS) (δ = 0.00 ppm) or CHCl (δ =
H
3
H
1
3
7
.25 ppm). C NMR spectra were recorded on Bruker Avance 400 (100 MHz) spectrometer at
RT in CDCl ; chemical shifts (δ ppm) are reported relative to CDCl [δ = 77.00 ppm (central line
3
3
C
1
3
2 3
of triplet)]. In the C NMR, the nature of carbons (C, CH, CH and CH ) was determined by
recording the DEPT-135 spectra, and is given in parentheses and noted as s = singlet (for C), d =
1
doublet (for CH), t = triplet (for CH
2
) and q = quartet (for CH
3
). In the H-NMR, the following
abbreviations were used throughout: s = singlet, d = doublet, t = triplet, q = quartet, qui =
quintet, sept = septet, dd = doublet of doublets, m = multiplet and br. s = broad singlet. The
1
13
assignment of signals was confirmed by H, C CPD and DEPT spectra. High-resolution mass
spectra (HR-MS) were recorded on an Agilent 6538 UHD Q-TOF electron spray ionization (ESI)
mode and atmospheric pressure chemical ionization (APCI) modes. The microwave irradiation

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experiments were carried out in a dedicated CEM-Discover monomode microwave apparatus,
operating at a frequency of 2.45 GHz with continuous irradiation power from 0 to 300 W and
utilization of the standard absorbance level of 100 W. The reactions were carried out in 10 mL
glass vials fitted with Teflon septum. The reactions were irradiated at the required temperature
for the stipulated time and then cooled to ambient temperature with air jet cooling. Reactions
were monitored by TLC on silica gel using a combination of hexane and ethyl acetate as eluents.
Reactions were generally run under argon or nitrogen atmosphere. Solvents were distilled prior
to use; petroleum ether with a boiling range of 60 to 80 °C was used. Pd (dba) , and K CO were
2
3
2
3
purchased from Sigma-Aldrich and used as received. ortho-Iodophenols, ortho-iodoanilines,
TBAB (tetrabutylammonium bromide), 3-chloro-2-methylprop-1-ene and propiolic acids were
purchased from Sigma-Aldrich/TCI/local sources and used as received. Acme’s silica gel (60–120
mesh) was used for column chromatography (approximately 20 g per one gram of crude
material). It is worth noting that these sort of experimental procedures have already been
1
2g,13,14
published elsewhere.
GP (General Procedure for the Synthesis of 3,3’-Disubstituted Heterocyclic Compounds
/6/7): An oven dried 10 mL microwave tube fitted with teflon septum was equipped with a
5
magnetic stir bar. The vial was charged with ortho-iodoaryl allyl ethers 1 (or) ortho-iodophenyl
allyl amines 3 (or) ortho-iodophenyl enamides 4 (68-88 mg, 0.25 mmol), propiolic acids 2 (31-54
2 3 2 3
mg, 0.37 mmol), Pd (dba) (2.28 mg, 1 mol%), K CO (103.9 mg, 0.75 mmol) TBAB (80.5 mg, 0.37
mmol), followed by solvent water (0.5mL), at room temperature. The resultant reaction mixture
was then subjected to microwave irradiation at 100 °C for 10 min (300 W, closed vessel).
Progress of the reaction was monitored by TLC till the reaction is completed. The mixture was
cooled to room temperature, quenched with aqueous NaHCO solution and extracted with
3
ethyl acetate (3 × 10 mL). The organic layers were washed with saturated NaCl solution, dried
(
Na SO ) and filtered. Evaporation of the solvent(s) under reduced pressure and purification of
2 4
the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate),
furnished the 3,3’-disubstituted heterocyclic compounds 5/6/7 (80‒98%) as oil.
3-Methyl-5-phenyl-3-(3-phenylprop-2-ynyl)-2,3-dihydro-1-benzofuran (5ea): GP was carried
out with 3-iodo-1,1'-biphenyl-4-yl 2-methylprop-2-enyl ether 1e (87.5 mg, 0.25 mmol), 3-

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phenylprop-2-ynoic acid 2a (54.7 mg, 0.37 mmol), Pd (dba) (2.28 mg, 1 mol%), TBAB (80.5 mg,
2
3
0
.25 mmol), K CO (103.9mg, 0.75 mmol) water (0.5 mL), under microwave irradiation (100 °C,
2
3
10 min, 300 W, closed vessel). Purification of the crude material by silica gel column
chromatography (petroleum ether/ethyl acetate, 100:0 to 97:3) furnished the
dihydrobenzofuran 5ea (72.9 mg, 90%) as a light yellow oily compound, [TLC control (petroleum
-
1
ether/ethyl acetate 99:1), R (1e)=0.8, R (5ea)=0.7, UV detection]. IR (MIR-ATR, 4000–600 cm ):
f
f
-
1 1
νmax=2960, 1605, 1482, 1375, 1224, 1067, 979, 813, 757, 693 cm . H NMR (CDCl , 400 MHz):
3
δ=7.57–7.49 (m, 2H, Ar–H), 7.47 (d, 1H, J = 2.0 Hz, Ar–H), 7.44–7.34 (m, 5H, Ar–H), 7.33–7.24
(
m, 4H, Ar–H), 6.88 (d, 1H, J = 8.3 Hz, Ar–H), 4.60 (d, J = 8.8 Hz, 1H, OCH H ), 4.30 (d, J = 8.8 Hz,
A B
1
3
1
H, OCH H ), 2.73 (s, 2H, CH ), 1.59 (s, 3H, CH ) ppm. C NMR (CDCl , 100 MHz): δ=159.2 (s,
A B 2 3 3
Ar–C), 141.3 (s, Ar–C), 134.6 (s, Ar–C), 134.2 (s, Ar–C), 131.6 (d, 2 × Ar–CH), 128.7 (d, 2 × Ar–
CH), 128.3 (d, 2 × Ar–CH), 127.9 (d, Ar–CH), 127.6 (d, Ar–CH), 126.8 (d, 2 × Ar–CH), 126.6 (d, Ar–
CH), 123.4 (s, Ar–C), 122.0 (d, Ar–CH), 109.9 (d, Ar–CH), 86.7 (s, C≡C), 82.8 (t, OCH ), 82.7 (s,
2
C≡C), 45.4 (s, C), 31.6 (t, CH ), 24.2 (q, CH ) ppm. HR-MS (ESI+) m/z calculated for
2
3
+
+
[
C
24
H
20KO] =[M+K] : 363.1146; found 363.1116.
3-But-2-ynyl-3-methyl-2,3-dihydro-1-benzofuran (5ab): GP was carried out with 1-iodo-2-[(2-
methylprop-2-enyl)oxy]benzene 1a (68.2 mg, 0.25 mmol), but-2-ynoic acid 2b (32 mg, 0.37
mmol), Pd (dba) (2.28 mg, 1 mol%), TBAB (80.5 mg, 0.25 mmol), K CO (103.9 mg, 0.75 mmol)
2
3
2
3
water (0.5 mL), under microwave irradiation (100 °C, 10 min, 300 W, closed vessel). Purification
of the crude material by silica gel column chromatography (petroleum ether/ethyl acetate,
100:0 to 99:1) furnished the dihydrobenzofuran 5ab (38.5 mg, 83%) as a light yellow oily
compound, [TLC control (petroleum ether/ethyl acetate 100:0), R (1a)=0.9, R (5ab)=0.8, UV
f
f
-
1
detection]. IR (MIR-ATR, 4000–600 cm ): νmax=2964, 2928, 2881, 1608, 1478, 1377, 1314, 1227,
-
1 1
1
7
7
2
175, 1123, 981, 872, 815, 766, 700 cm . H NMR (CDCl
.12 (dd, J = 7.8 and 1.4 Hz, 1H, Ar-H), 6.87 (ddd, J = 7.3, 7.3 and 1.0 Hz, 1H, Ar–H), 6.78 (d, J =
.8 Hz, 1H, Ar–H), 4.47 (d, J = 8.8 Hz, 1H, OCH ), 4.17 (d, J = 8.8 Hz, 1H, OCH ), 2.40 (q, J =
.5 Hz, 2H, CH ), 1.79 (t, J = 2.5 Hz, 3H, CH ), 1.44 (s, 3H, CH ) ppm. C NMR (CDCl , 100 MHz):
3
, 400 MHz): δ=7.19–7.12 (m, 1H, Ar–H),
A
H
B
A B
H
1
3
2
3
3
3
δ=159.4 (s, Ar–C), 134.3 (s, Ar–C), 128.4 (d, Ar–CH), 122.8 (d, Ar–CH), 120.4 (d, Ar–CH), 109.7 (d,

ACCEPTED MANUSCRIPT
Ar–CH), 82.3 (t, OCH ), 77.5 (s, C≡C), 75.7 (s, C≡C), 45.1 (s, C), 30.8 (t, CH ), 24.3 (q, CH ), 3.4 (q,
2
2
3
+
+
CH ) ppm. HR-MS (ESI+) m/z calculated for [C H NO] =[M+NH ] : 204.1383; found 204.1386.
3
13 18
4
3-But-2-ynyl-3,5-dimethyl-2,3-dihydro-1-benzofuran (5bb): GP was carried out with 2-iodo-4-
methyl-1-[(2-methylprop-2-enyl)oxy]benzene 1b (72 mg, 0.25 mmol), but-2-ynoic acid 2b (32
mg, 0.37 mmol), Pd (dba) (2.28 mg, 1 mol%), TBAB (80.5 mg, 0.25 mmol), K CO (103.9 mg,
2
3
2
3
0.75 mmol) water (0.5 mL) , under microwave irradiation (100 °C, 10 min, 300 W, closed
vessel). Purification of the crude material by silica gel column chromatography (petroleum
ether/ethyl acetate, 100:0 to 99:1) furnished the dihydrobenzofuran 5bb (40 mg, 82%) as a light
yellow oily compound, [TLC control (petroleum ether/ethyl acetate 100:0), R (1b)=0.9,
f
-
1
R (5bb)=0.8, UV detection]. IR (MIR-ATR, 4000–600 cm ): νmax=2964, 1608, 1478, 1376, 1230,
f
-1 1
1
175, 981, 874, 815, 766, 700 cm . H NMR (CDCl , 400 MHz): δ=6.94 (s, 1H, Ar–H), 6.93 (d, J =
3
8
.8 Hz, 1H, Ar-H), 6.68 (dd, J = 6.8 and 1.9 Hz, 1H, Ar–H), 4.46 (d, J = 8.8 Hz, 1H, OCH
), 2.39 (q, J = 2.5 Hz, 2H, CH ), 2.29 (s, 3H, CH ), 1.79 (t, J = 2.5 Hz, 3H,
, 100 MHz): δ=157.3 (s, Ar–C), 134.3 (s, Ar–C), 129.7
), 77.5 (s, C≡C), 75.8
) ppm. HR-MS (ESI+) m/z
A B
H ), 4.14
(d, J = 8.80 Hz, 1H, OCH
A
H
B
2
3
1
3
3 3 3
CH ), 1.42 (s, 3H, CH ) ppm. C NMR (CDCl
(s, Ar–C), 128.7 (d, Ar–CH), 123.3 (d, Ar–CH), 109.2 (d, Ar–CH), 82.3 (t, OCH
2
(s, C≡C), 45.1 (s, C), 30.8 (t, CH
2
3 3 3
), 24.2 (q, CH ), 20.9 (q, CH ), 3.4 (q, CH
+
+
calculated for [C H O] =[M+H] : 201.1274; found 201.1271.
1
4 17
3-But-2-ynyl-5-ethyl-3-methyl-2,3-dihydro-1-benzofuran (5cb): GP was carried out with 4-
ethyl-2-iodo-1-[(2-methylprop-2-enyl)oxy]benzene 1c (75.5 mg, 0.25 mmol), but-2-ynoic acid 2b
(
32 mg, 0.37 mmol), Pd (dba) (2.28 mg, 1 mol%), TBAB (80.5 mg, 0.25 mmol), K CO (103.9 mg,
2 3 2 3
0.75 mmol) water (0.5 mL), under microwave irradiation (100 °C, 10 min, 300 W, closed vessel).
Purification of the crude material by silica gel column chromatography (petroleum ether/ethyl
acetate, 100:0 to 99:1) furnished the dihydrobenzofuran 5cb (42.9 mg, 81%) as a light yellow
oily compound, [TLC control (petroleum ether/ethyl acetate 100:0), R
f
(1c)=0.9, R
max=2964, 2883, 1608, 1478, 1377, 1230, 1176, 981,
, 400 MHz): δ=6.97 (s, 1H, Ar–H), 6.95 (dd, J = 8.3 and 1.5 Hz,
H, Ar–H), 6.70 (d, J = 8.3 Hz, 1H, Ar–H), 4.45 (d, J = 8.8 Hz, 1H, OCH H ), 4.15 (d, J = 8.8 Hz, 1H,
f
(5cb)=0.8, UV
-
1
detection]. IR (MIR-ATR, 4000–600 cm ):
ν
-
1 1
8
15, 766, 700 cm . H NMR (CDCl
3
1
A
B
OCH H ), 2.59 (q, J = 7.6 Hz, 2H, CH ), 2.39 (q, J = 2.5 Hz, 2H, CH ), 1.80 (t, J = 2.7 Hz, 3H, CH ),
A
B
2
2
3

ACCEPTED MANUSCRIPT
1
3
1
.43 (s, 3H, CH ), 1.21 (t, 3H, J = 7.6 Hz) ppm. C NMR (CDCl , 100 MHz): δ=157.5 (s, Ar–C),
3 3
136.4 (s, Ar–C), 134.3 (s, Ar–C), 127.6 (d, Ar–CH), 122.2 (d, Ar–CH), 109.2 (d, Ar–CH), 82.4 (t,
OCH
CH ), 3.4 (q, CH
32.1695.
2
), 77.4 (s, C≡C), 75.8 (s, C≡C), 45.1 (s, C), 30.8 (t, CH
2
), 28.4 (t, CH
2
3
), 24.1 (q, CH ), 16.0 (q,
+
+
3
3
). HR-MS (ESI+) m/z calculated for [C15
H
22NO] =[M+NH
4
] : 232.1696; found
2
5-tert-Butyl-3-but-2-ynyl-3-methyl-2,3-dihydro-1-benzofuran (5db): GP was carried out with
4-tert-butyl-2-iodo-1-[(2-methylprop-2-enyl)oxy]benzene 1d (82 mg, 0.25 mmol), but-2-ynoic
acid 2b (32 mg, 0.37 mmol), Pd (dba) (2.28 mg, 1 mol%), TBAB (80.5 mg, 0.25 mmol), K CO
3
2
3
2
(
103.9 mg, 0.75 mmol) water (0.5 mL), under microwave irradiation (100 °C, 10 min, 300 W,
closed vessel). Purification of the crude material by silica gel column chromatography
petroleum ether/ethyl acetate, 100:0 to 98:2) furnished the dihydrobenzofuran 5db (49.8 mg,
(
83%) as a light yellow oily compound, [TLC control (petroleum ether/ethyl acetate 100:0),
-
1
R
f
(1d)=0.9, R
f
(5db)=0.8, UV detection]. IR (MIR-ATR, 4000–600 cm ):
ν
max=2962, 2922, 2876,
, 400 MHz):
-
1 1
1
611, 1485, 1375, 1219, 1062, 981, 886, 817, 768, 707, 626 cm . H NMR (CDCl
3
δ=7.19 (d, J = 2.0 Hz, 1H, Ar–H), 7.15 (dd, J = 8.3 and 2.0 Hz, 1H, Ar–H), 6.70 (d, J = 8.3 Hz, 1H,
Ar–H), 4.42 (d, J = 8.8 Hz, 1H, OCH H ), 4.15 (d, J = 8.8 Hz, 1H, OCH H ), 2.39 (q, J = 2.4 Hz, 2H,
A
B
A B
1
3
CH ), 1.80 (t, J = 2.4 Hz, 3H, CH ), 1.44 (s, 3H, CH ), 1.30 (s, 9H, 3 × CH ) ppm. C NMR (CDCl3,
2
3
3
3
100 MHz): δ=157.2 (s, Ar–C), 143.4 (s, Ar–C), 133.8 (s, Ar–C), 125.1 (d, Ar–CH), 119.8 (d, Ar–CH),
1
08.8 (d, Ar–CH), 82.6 (t, OCH ), 77.4 (s, C≡C), 75.9 (s, C≡C), 45.2 (s, C), 34.4 (s, C), 31.7 (q, 3 ×
2
CH ), 30.9 (t, CH ), 23.9 (q, CH ), 3.4 (q, CH ) ppm. HR-MS (ESI+) m/z calculated for
3
2
3
3
+
+
[
C H NaO] =[M+Na] : 265.1563; found 265.1548.
1
7 22
3-But-2-ynyl-5-fluoro-3-methyl-2,3-dihydro-1-benzofuran (5fb): GP was carried out with 4-
fluoro-2-iodo-1-[(2-methylprop-2-enyl)oxy]benzene 1f (73 mg, 0.25 mmol), but-2-ynoic acid 2b
(
32 mg, 0.37 mmol), Pd (dba) (2.28 mg, 1 mol%), TBAB (80.5 mg, 0.25 mmol), K CO (103.9 mg,
2 3 2 3
0.75 mmol) water (0.5 mL), under microwave irradiation (100 °C, 10 min, 300 W, closed vessel).
Purification of the crude material by silica gel column chromatography (petroleum ether/ethyl
acetate, 100:0 to 99:1) furnished the dihydrobenzofuran 5fb (40.8 mg, 80%) as a light yellow
oily compound, [TLC control (petroleum ether/ethyl acetate 100:0), R (1f)=0.9, R (5fb)=0.8, UV
f
f

ACCEPTED MANUSCRIPT
-
1
detection]. IR (MIR-ATR, 4000–600 cm ): νmax=2965, 2919, 1615, 1477, 1377, 1311, 1240, 1172,
-1 1
1
106, 981, 918, 867, 808, 786, 713 cm . H NMR (CDCl , 400 MHz): δ=6.85 (dd, J = 8.1 and 2.7
3
Hz, 1H, Ar–H), 6.80 (ddd, J = 8.8, 8.8 and 2.7 Hz, 1H, Ar–H), 6.67 (dd, J = 8.6 and 4.2 Hz, 1H, Ar–
H), 4.45 (d, J = 8.8 Hz, 1H, OCH ), 4.17 (d, J = 8.8 Hz, 1H, OCH ), 2.38 (q, J = 2.4 Hz, 2H, CH ),
) ppm. C NMR (CDCl , 100 MHz): δ=157.4 (d, J =
37.7 Hz, Ar–C), 155.2 (s, Ar–C), 135.7 (d, J = 8.1 Hz, Ar–C), 114.4 (d, J = 24.1 Hz, Ar–CH), 110.1
A
H
B
A
H
B
2
1
3
1.78 (t, J = 2.4 Hz, 3H, CH
3
), 1.41 (s, 3H, CH
3
3
2
(
d, J = 24.2 Hz, Ar–CH), 109.8 (d, J = 8.1 Hz, Ar–CH), 82.8 (t, OCH ), 77.9 (s, C≡C), 75.2 (s, C≡C),
2
4
5.4 (d, J = 1.5 Hz, C), 30.6 (t, CH ), 24.1 (q, CH ), 3.4 (q, CH ) ppm. HR-MS (ESI+) m/z calculated
2 3 3
+
+
for [C H F] =[M]+[−H O] : 187.0918; found 187.0911.
1
3
12
2
3
-But-2-ynyl-5-chloro-3-methyl-2,3-dihydro-1-benzofuran (5gb): GP was carried out with 4-
chloro-2-iodo-1-[(2-methylprop-2-enyl)oxy]benzene 1g (77 mg, 0.25 mmol), but-2-ynoic acid 2b
32 mg, 0.37 mmol), Pd (dba) (2.28 mg, 1 mol%), TBAB (80.5 mg, 0.25 mmol), K CO (103.9 mg,
.75 mmol) water (0.5 mL), under microwave irradiation (100 °C, 10 min, 300 W, closed vessel).
(
2
3
2
3
0
Purification of the crude material by silica gel column chromatography (petroleum ether/ethyl
acetate, 100:0 to 99:1) furnished the dihydrobenzofuran 5gb (44.5 mg, 81%) as a light yellow
oily compound, [TLC control (petroleum ether/ethyl acetate 100:0), R (1g)=0.9, R (5gb)=0.8, UV
f
f
-
1
detection]. IR (MIR-ATR, 4000–600 cm ): νmax=2960, 2923, 2879, 1607, 1473, 1376, 1227, 1173,
-
1 1
1
122, , 980, 872, 814, 765, 700 cm . H NMR (CDCl , 400 MHz): δ=7.08 (d, J = 2.4 Hz, 1H, Ar–H),
3
7.06 (dd, J = 8.8 and 2.4 Hz, 1H, Ar–H), 6.69 (d, J = 8.8 Hz, 1H, Ar–H), 4.47 (d, J = 8.8 Hz, 1H,
OCH H ), 4.18 (d, J = 8.8 Hz, 1H, OCH H ), 2.38 (q, J = 2.4 Hz, 2H, CH ), 1.78 (t, J = 2.4 Hz, 3H,
A
B
A
B
2
1
3
CH ), 1.41 (s, 3H, CH ) ppm. C NMR (CDCl , 100 MHz): δ=158.1 (s, Ar–C), 136.2 (s, Ar–C), 128.2
3
3
3
(
d, Ar–CH), 125.1 (s, Ar–C), 123.2 (d, Ar–CH), 110.7 (d, Ar–CH), 82.8 (t, OCH ), 78.0 (s, C≡C), 75.2
2
(
s, C≡C), 45.4 (s, C), 30.7 (t, CH ), 24.2 (q, CH ), 3.4 (q, CH ) ppm. HR-MS (ESI+) m/z calculated
2
3
3
+
+
for [C13H13ClO] =[M] : 220.0649; found 220.0661.
5
-Bromo-3-but-2-ynyl-3-methyl-2,3-dihydro-1-benzofuran (5hb): GP was carried out with 4-
bromo-2-iodo-1-[(2-methylprop-2-enyl)oxy]benzene 1h (88 mg, 0.25 mmol), but-2-ynoic acid
b (32 mg, 0.37 mmol), Pd (dba) (2.28 mg, 1 mol%), TBAB (80.5 mg, 0.25 mmol), K CO (103.9
2
2
3
2
3
mg, 0.75 mmol) water (0.5 mL), under microwave irradiation (100 °C, 10 min, 300 W, closed

ACCEPTED MANUSCRIPT
vessel). Purification of the crude material by silica gel column chromatography (petroleum
ether/ethyl acetate, 100:0 to 99:1) furnished the dihydrobenzofuran 5hb (52.8 mg, 80%) as a
light yellow oily compound, [TLC control (petroleum ether/ethyl acetate 100:0), R
f
(1h)=0.9,
max=3038, 2923, 1611, 1484, 1452,
3
336, 1187, 1098, 982, 763, 696 cm . H NMR (CDCl , 400 MHz): δ=7.22 (s, 1H, Ar–H), 7.20 (dd,
-
1
f
R (5hb)=0.8, UV detection]. IR (MIR-ATR, 4000–600 cm ): ν
-
1 1
1
J = 7.8 and 2.0 Hz, 1H, Ar–H), 6.65 (dd, J = 7.8 and 1.0 Hz, 1H, Ar–H), 4.46 (d, J = 8.8 Hz, 1H,
OCH H ), 4.17 (d, J = 8.8 Hz, 1H, OCH H ), 2.37 (q, J = 2.2 Hz, 2H, CH ), 1.78 (t, J = 2.4 Hz, 3H,
A
B
A
B
2
1
3
CH ), 1.41 (s, 3H, CH ) ppm. C NMR (CDCl , 100 MHz): δ=158.6 (s, Ar–C), 136.7 (s, Ar–C), 131.1
3
3
3
(
d, Ar–CH), 126.1 (d, Ar–CH), 112.2 (s, Ar–C), 111.3 (d, Ar–CH), 82.7 (t, OCH ), 78.0 (s, C≡C), 75.2
2
(
s, C≡C), 45.4 (s, C), 30.7 (t, CH ), 24.2 (q, CH ), 3.4 (q, CH ) ppm. HR-MS (ESI+) m/z calculated
2
3
3
7
9
+
+
81
+
+
for [C H BrO] =[M+H] : 265.0223; found 265.0227; [C H BrO] =[M+H] : 267.0203; found
1
3
14
13 14
265.0204.
3
-Methyl-3-pent-2-ynyl-2,3-dihydro-1-benzofuran (5ac): GP was carried out with 1-iodo-2-
(2-methylprop-2-enyl)oxy]benzene 1a (68.2 mg, 0.25 mmol), pent-2-ynoic acid 2c (37 mg, 0.37
mmol), Pd (dba) (2.28 mg, 1 mol TBAB (80.5 mg, 0.25 mmol), K CO (103.9 mg, 0.75 mmol)
[
2
3
2
3
water (0.5 mL), under microwave irradiation (100 °C, 10 min, 300 W, closed vessel). Purification
of the crude material by silica gel column chromatography (petroleum ether/ethyl acetate,
100:0 to 99:1) furnished the dihydrobenzofuran 5ac (41.1 mg, 84%) as a light yellow oily
compound, [TLC control (petroleum ether/ethyl acetate 100:0), R (1a)=0.9, R (5ac)=0.8, UV
f
f
-
1
detection]. IR (MIR-ATR, 4000–600 cm ): νmax=2963, 2881, 1480, 1379, 1318, 1240, 1175, 1105,
-
1 1
9
84, 920, 867, 810, 715 cm . H NMR (CDCl , 400 MHz): δ=7.15 (dd, J = 7.3 and 1.0 Hz, 1H, Ar–
3
H), 7.12 (dd, J = 7.3 and 1.5 Hz, 1H, Ar–H), 6.87 (ddd, J = 7.3, 7.3 and 1.0 Hz, 1H, Ar–H), 6.79 (d, J
=
7.3 Hz, 1H, Ar–H), 4.47 (d, J = 8.8 Hz, 1H, OCH
.5 Hz, 2H, CH ), 2.23–2.08 (m, 2H, CH ), 1.45 (s, 3H, CH
, 100 MHz): δ=159.4 (s, Ar–C), 134.3 (s, Ar–C), 128.4 (d, Ar–CH), 122.9 (d, Ar–CH),
20.4 (d, Ar–CH), 109.7 (d, Ar–CH), 83.8 (s, C≡C), 82.3 (t, OCH ), 75.9 (s, C≡C), 45.1 (s, C), 30.9 (t,
) ppm. HR-MS (ESI+) m/z calculated for
A
H
B
), 4.16 (d, J = 8.8 Hz, 1H, OCH
A B
H ), 2.41 (t, J =
1
3
2
2
2
3
), 1.12 (t, J = 7.3 Hz, 3H, CH
3
) ppm. C
NMR (CDCl
3
1
2
CH
2
), 24.2 (q, CH
3
3 2
), 14.2 (q, CH ), 12.4 (t, CH
+
+
[
C H N] =[M+NH ] +[–H O] : 200.1434; found 200.1425.
1
4
18
4
2

ACCEPTED MANUSCRIPT
3,5-Dimethyl-3-pent-2-ynyl-2,3-dihydro-1-benzofuran (5bc): GP was carried out with 2-iodo-
4
-methyl-1-[(2-methylprop-2-enyl)oxy]benzene 1b (72 mg, 0.25 mmol), pent-2-ynoic acid 2c (37
mg, 0.37 mmol), Pd (dba) (2.28 mg, 1 mol%), TBAB (80.5 mg, 0.25 mmol), K CO (103.9 mg,
.75 mmol) water (0.5 mL), under microwave irradiation (100 °C, 10 min, 300 W, closed vessel).
2
3
2
3
0
Purification of the crude material by silica gel column chromatography (petroleum ether/ethyl
acetate, 100:0 to 98:2) furnished the dihydrobenzofuran 5bc (46.6 mg, 88%) as a light yellow
oily compound, [TLC control (petroleum ether/ethyl acetate 100:0), R (1b)=0.9, R (5bc)=0.8, UV
f
f
-
1
detection]. IR (MIR-ATR, 4000–600 cm ): νmax=2962, 2922, 2876, 1612, 1485, 1375, 1217, 1136,
-
1 1
1
062, 981, 886, 817, 770, 711, 620 cm . H NMR (CDCl , 400 MHz): δ=6.95 (s, 1H, Ar–H), 6.92
3
(
dd, J = 8.3 and 2.0 Hz, 1H, Ar–H), 6.67 (d, J = 8.3 Hz, 1H, Ar–H), 4.44 (d, J = 8.8 Hz, 1H, OCH H ),
A B
4
.14 (d, J = 8.8 Hz, 1H, OCH H ), 2.39 (t, J = 2.4 Hz, 2H, CH ), 2.28 (s, 3H, CH ), 2.21–2.12 (m, 2H,
A
B
2
3
1
3
CH ), 1.42 (s, 3H, CH ), 1.11 (t, J = 7.6 Hz, 3H, CH ) ppm. C NMR (CDCl , 100 MHz): δ=157.3 (s,
2
3
2
3
Ar–C), 134.3 (s, Ar–C), 129.6 (s, Ar–C), 128.7 (d, Ar–CH), 123.5 (d, Ar–CH), 109.2 (d, Ar–CH), 83.7
(
s, C≡C), 82.4 (t, OCH
q, CH ), 12.4 (t, CH
2
), 76.0 (s, C≡C), 45.1 (s, C), 30.8 (t, CH
2
), 24.1 (q, CH
3
3
), 20.9 (q, CH ), 14.2
+
+
(
3
2
) ppm. HR-MS (ESI+) m/z calculated for [C15
H
22NO] =[M+NH
4
] : 232.1696;
found 232.1688.
3
-Methyl-3-pent-2-ynyl-5-phenyl-2,3-dihydro-1-benzofuran (5ec): GP was carried out with 3-
iodo-1,1'-biphenyl-4-yl 2-methylprop-2-enyl ether 1e (87.5 mg, 0.25 mmol), pent-2-ynoic acid
c (37 mg, 0.37 mmol), Pd (dba) (2.28 mg, 1 mol%), TBAB (80.5 mg, 0.25 mmol), K CO (103.9
2
2
3
2
3
mg, 0.75 mmol) water (0.5 mL), under microwave irradiation (100 °C, 10 min, 300 W, closed
vessel). Purification of the crude material by silica gel column chromatography (petroleum
ether/ethyl acetate, 100:0 to 98:2) furnished the dihydrobenzofuran 5ec (56.5 mg, 82%) as a
light yellow oily compound, [TLC control (petroleum ether/ethyl acetate 100:0), R
f
(1e)=0.8,
max=2962, 2922, 1719, 1605, 1484,
375, 1226, 1068, 980, 888, 813, 757, 693 cm . H NMR (CDCl , 400 MHz): δ=7.57–7.50 (m, 2H,
Ar–H), 7.44–7.36 (m, 2H, Ar–H), 7.38 (s, 1H, Ar-H), 7.37 (dd, J = 7.9 and 2.0 Hz, 1H, Ar-H), 7.28
-1
f
R (5ec)=0.7, UV detection]. IR (MIR-ATR, 4000–600 cm ): ν
-
1 1
1
3
(
m, 1H, Ar–H), 6.84 (dd, J = 8.8 and 0.7 Hz, 1H, Ar–H), 4.52 (d, J = 8.8 Hz, 1H, OCH H ), 4.22 (d, J
A B
=
1
8.8 Hz, 1H, OCH H ), 2.46 (t, J = 2.4 Hz, 2H, CH ), 2.23–2.12 (m, 2H, CH ), 1.49 (s, 3H, CH ),
A B 2 2 3
1
3
.11 (t, J = 7.3 Hz, 3H, CH ) ppm. C NMR (CDCl , 100 MHz): δ=159.2 (s, Ar–C), 141.4 (s, Ar–C),
3
3

ACCEPTED MANUSCRIPT
135.0 (s, Ar–C), 134.1 (s, Ar–C), 128.7 (d, 2 × Ar–CH), 127.5 (d, Ar–CH), 126.8 (d, Ar–CH), 126.5
(
d, Ar–CH), 121.9 (d, Ar–CH), 109.8 (d, Ar–CH), 83.9 (s, C≡C), 82.8 (t, OCH ), 75.9 (s, C≡C), 45.2
2
(
s, C), 30.8 (t, CH
2
3 3 2
), 24.3 (q, CH ), 14.3 (q, CH ), 12.4 (t, CH ) ppm. HR-MS (ESI+) m/z calculated
+
+
for [C20
H
24NO] =[M+NH
4
] : 294.1852; found 294.1840.
5-Fluoro-3-methyl-3-pent-2-ynyl-2,3-dihydro-1-benzofuran (5fc): GP was carried out with 4-
fluoro-2-iodo-1-[(2-methylprop-2-enyl)oxy]benzene 1f (73 mg, 0.25 mmol), pent-2-ynoic acid 2c
(
37 mg, 0.37 mmol), Pd (dba) (2.28 mg, 1 mol%), TBAB (80.5 mg, 0.25 mmol), K CO (103.9 mg,
2
3
2
3
0.75 mmol) water (0.5 mL), under microwave irradiation (100 °C, 10 min, 300 W, closed vessel).
Purification of the crude material by silica gel column chromatography (petroleum ether/ethyl
acetate, 100:0 to 99:1) furnished the dihydrobenzofuran 5fc (43.7 mg, 81%) as a light yellow
oily compound, [TLC control (petroleum ether/ethyl acetate 100:0), R
f
(1f)=0.9, R
max=3035, 2923, 1654, 1611, 1485, 1451, 1336, 1186,
097, 982, 881, 817, 763, 696 cm . H NMR (CDCl , 400 MHz): δ=6.86 (dd, J = 8.1 and 2.7 Hz,
f
(5fc)=0.8, UV
-
1
detection]. IR (MIR-ATR, 4000–600 cm ):
ν
-
1 1
1
1
4
2
3
H, Ar–H), 6.80 (ddd, J = 8.8, 8.8 and 2.9 Hz, 1H, Ar–H), 6.67 (dd, J = 8.8 and 3.9 Hz, 1H, Ar–H),
.45 (d, J = 8.8 Hz, 1H, OCH H ), 4.18 (d, J = 8.8 Hz, 1H, OCH H ), 2.39 (t, J = 2.4 Hz, 2H, CH ),
A
B
A
B
2
1
3
.22–2.11 (m, 2H, CH ), 1.42 (s, 3H, CH ), 1.10 (t, J = 7.3 Hz, 3H, CH ) ppm. C NMR (CDCl , 100
2
3
3
3
MHz): δ=157.4 (d, J = 236.9 Hz, Ar–C), 155.3 (s, Ar–C), 135.7 (d, J = 8.1 Hz, Ar–C), 114.4 (d, J =
4.2 Hz, Ar–CH), 110.1 (d, J = 24.9 Hz, Ar–CH), 109.8 (d, J = 8.1 Hz, Ar–CH), 84.1 (s, C≡C), 82.8 (t,
OCH ), 75.5 (s, C≡C), 45.5 (d, J = 2.0 Hz, C), 30.7 (t, CH ), 24.0 (q, CH ), 14.2 (q, CH ), 12.3 (t, CH )
2
2
2
3
3
2
+
+
ppm. HR-MS (ESI+) m/z calculated for [C H F] =[M]+[–H O] : 200.0966; found 200.1007.
1
4
13
2
5
-tert-Butyl-3-hex-2-ynyl-3-methyl-2,3-dihydro-1-benzofuran (5dd): GP was carried out with
-tert-butyl-2-iodo-1-[(2-methylprop-2-enyl)oxy]benzene 4d (75.5 mg, 0.25 mmol), hex-2-ynoic
acid 2d (42 mg, 0.37 mmol), Pd (dba) (2.28 mg, 1 mol%), TBAB (80.5 mg, 0.25 mmol), K CO
103.9 mg, 0.75 mmol) water (0.5 mL), under microwave irradiation (100 °C, 10 min, 300 W,
closed vessel). Purification of the crude material by silica gel column chromatography
petroleum ether/ethyl acetate, 100:0 to 99:1) furnished the dihydrobenzofuran 5dd (56.9 mg,
5%) as a light yellow oily compound, [TLC control (petroleum ether/ethyl acetate 100:0),
4
2
3
2
3
(
(
8
-
1
R (4d)=0.9, R (5dd)=0.8, UV detection]. IR (MIR-ATR, 4000–600 cm ): νmax=2962, 2884, 1480,
f
f

ACCEPTED MANUSCRIPT
-1
1
1
241, 1176, 985, 869, 807 cm . H NMR (CDCl , 400 MHz): δ=7.18 (d, J = 2.0 Hz, 1H, Ar–H), 7.15
3
(
dd, J = 8.3 and 2.0 Hz, 1H, Ar–H), 6.70 (d, J = 8.3 Hz, 1H, Ar–H), 4.43 (d, J = 8.8 Hz, 1H, OCH
A
H
B
),
4.15 (d, J = 8.8 Hz, 1H, OCH
A
B
H ), 2.42 (t, J = 2.2 Hz, 2H, CH
), 2.18–2.10 (m, 2H, CH ), 1.50 (sext, J
2 2
1
3
=
7.3 Hz, 2H, CH ), 1.45 (s, 3H, CH
2
3
), 1.29 (s, 9H, 3 × CH ), 0.95 (t, J = 7.3 Hz, 3H, CH ) ppm. C
3
3
NMR (CDCl , 100 MHz): δ=157.2 (s, Ar–C), 143.3 (s, Ar–C), 133.8 (s, Ar–C), 125.1 (d, Ar–CH),
3
1
19.8 (d, Ar–CH), 108.8 (d, Ar–CH), 82.6 (t, OCH ), 82.1 (s, C≡C), 76.9 (s, C≡C), 45.2 (s, C), 34.4 (s,
2
C), 31.7 (q, 3 × CH ), 30.9 (t, CH ), 24.0 (q, CH ), 22.4 (t, CH ), 20.7 (t, CH ), 13.5 (q, CH ) ppm.
3
2
3
2
2
3
+
+
HR-MS (ESI+) m/z calculated for [C H NO] =[M+NH ] : 288.2322; found 288.2340.
1
9
30
4
3
-Hex-2-ynyl-3-methyl-5-phenyl-2,3-dihydro-1-benzofuran (5ed): GP was carried out with 3-
iodo-1,1'-biphenyl-4-yl 2-methylprop-2-enyl ether 1e (87.5 mg, 0.25 mmol), hex-2-ynoic acid 2d
42 mg, 0.37 mmol), Pd (dba) (2.28 mg, 1 mol%), TBAB (80.5 mg, 0.25 mmol), K CO (103.9 mg,
.75 mmol) water (0.5 mL), under microwave irradiation (100 °C, 10 min, 300 W, closed vessel).
(
2
3
2
3
0
Purification of the crude material by silica gel column chromatography (petroleum ether/ethyl
acetate, 100:0 to 98:2) furnished the dihydrobenzofuran 5ed (63.3 mg, 88%) as a light yellow
oily compound, [TLC control (petroleum ether/ethyl acetate 100:0), R (1e)=0.8, R (5ed)=0.7, UV
f
f
-1
detection]. IR (MIR-ATR, 4000–600 cm ): νmax=2962, 2923, 1606, 1485, 1375, 1226, 1068, 980,
-
1 1
8
2
6
90, 813, 758, 693 cm . H NMR (CDCl , 400 MHz): δ=7.59–7.49 (m, 2H, Ar–H), 7.45–7.35 (m,
3
H, Ar–H), 7.38 (s, 1H, Ar–H), 7.37 (dd, J = 7.6 and 2.0 Hz, 1H, Ar–H), 7.33–7.25 (m, 1H, Ar–H),
.84 (dd, J = 7.6 and 1.2 Hz, 1H, Ar–H), 4.53 (d, J = 8.8 Hz, 1H, OCH H ), 4.23 (d, J = 8.8 Hz, 1H,
A
B
OCH H ), 2.47 (t, J = 2.0 Hz, 2H, CH ), 2.17–2.10 (m, 2H, CH ), 1.48 (sext, J = 7.3 Hz, 2H, CH ),
A
B
2
2
2
1
3
1
1
2
7
.49 (s, 3H, CH
3
), 0.93 (t, J = 7.3 Hz, 3H, CH
3
) ppm. C NMR (CDCl
3
, 100 MHz): δ=159.2 (s, Ar–C),
41.4 (s, Ar–C), 135.0 (s, Ar–C), 134.1 (s, Ar–C), 128.6 (d, 2 × Ar–CH), 127.5 (d, Ar–CH), 126.8 (d,
× Ar–CH), 126.5 (d, Ar–CH), 121.8 (d, Ar–CH), 109.8 (d, Ar–CH), 82.7 (t, OCH ), 82.4 (s, C≡C),
3
), 13.4 (q, CH )
2
7.0 (s, C≡C), 45.2 (s, C), 30.9 (t, CH
2
), 24.3 (q, CH
3
), 22.4 (t, CH
2
), 20.7 (t, CH
2
+
+
ppm. HR-MS (ESI+) m/z calculated for [C21
H
23O] =[M+H] : 291.1743; found 291.1734.
5
-Fluoro-3-hex-2-ynyl-3-methyl-2,3-dihydro-1-benzofuran (5fd): GP was carried out with 4-
fluoro-2-iodo-1-[(2-methylprop-2-enyl)oxy]benzene 1f (73 mg, 0.25 mmol), hex-2-ynoic acid 2d
42 mg, 0.37 mmol), Pd (dba) (2.28 mg, 1 mol%), TBAB (80.5 mg, 0.25 mmol), K CO (103.9 mg,
(
2
3
2
3

ACCEPTED MANUSCRIPT
0.75 mmol) water (0.5 mL), under microwave irradiation (100 °C, 10 min, 300 W, closed vessel).
Purification of the crude material by silica gel column chromatography (petroleum ether/ethyl
acetate, 100:0 to 99:1) furnished the dihydrobenzofuran 5fd (47.5 mg, 82%) as a light yellow
oily compound, [TLC control (petroleum ether/ethyl acetate 100:0), R
f
f
(1f)=0.9, R (5fd)=0.8, UV
-
1
detection]. IR (MIR-ATR, 4000–600 cm ):
νmax=3037, 2923, 1654, 1610, 1484, 1452, 1336, 1250,
-1 1
1
3
186, 1097, 981, 881, 817, 762, 695 cm . H NMR (CDCl , 400 MHz): δ=6.85 (dd, J = 8.1 and 2.7
Hz, 1H, Ar–H), 6.79 (ddd, J = 8.8, 8.8 and 2.4 Hz, 1H, Ar–H), 6.67 (dd, J = 8.6 and 4.2 Hz, 1H, Ar–
H), 4.46 (d, J = 8.8 Hz, 1H, OCH H ), 4.18 (d, J = 8.8 Hz, 1H, OCH H ), 2.41 (q, J = 2.5 and 1.0 Hz,
A
B
A B
2H, CH ), 2.15–2.08 (m, 2H, CH ), 1.48 (sext, J = 7.3 Hz , 2H, CH ), 1.42 (s, 3H, CH ), 0.94 (t, J =
2 2 2 3
1
3
7
.3 Hz, 3H, CH ) ppm. C NMR (CDCl , 100 MHz): δ=157.5 (d, J = 236.9 Hz, Ar–C), 155.3 (s, Ar–
3
3
C), 135.6 (d, J = 8.1 Hz, Ar–C), 114.4 (d, J = 24.2 Hz, Ar–CH), 110.1 (d, J = 24.2 Hz, Ar–CH), 109.8
(
(
[
d, J = 8.1 Hz, Ar–CH), 82.8 (t, OCH ), 82.6 (s, C≡C), 76.3 (s, C≡C), 45.5 (s, C), 30.7 (t, CH ), 24.1
2
2
q, CH ), 22.3 (t, CH ), 20.6 (t, CH ), 13.4 (q, CH ) ppm. HR-MS (ESI+) m/z calculated for
3
2
2
3
+
+
15 4
C H21FNO] =[M+NH ] : 250.1602; found 250.1609.
3-But-2-ynyl-1,3-dimethylindoline (6ab): GP was carried out with 2-iodo-N-methyl-N-(2-
methylallyl)aniline 3a (71.7 mg, 0.25 mmol), but-2-ynoic acid 2b (32 mg, 0.37 mmol), Pd (dba)
2
3
(
2.28 mg, 1 mol%), TBAB (80.5 mg, 0.25 mmol), K CO (103.9 mg, 0.75 mmol) water (0.5 mL),
2 3
under microwave irradiation (100 °C, 10 min, 300 W, closed vessel). Purification of the crude
material by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 95:5)
furnished the indoline 6ab (44.5 mg, 89%) as a light yellow oily compound, [TLC control
(
petroleum ether/ethyl acetate 100:0), R (3a)=0.8, R (6ab)=0.7, UV detection]. IR (MIR-ATR,
f f
-
1
4
000–600 cm ): νmax=2965, 2918, 2862, 2806, 1605, 1488, 1454, 1376, 1310, 1247, 1215, 1155,
-1 1
1
3
110, 1018, 966, 742 cm . H NMR (CDCl , 400 MHz): δ=7.10 (ddd, J = 7.8, 7.8 and 1.5 Hz, 1H,
Ar–H), 7.05 (dd, J = 7.3 and 1.0 Hz, 1H, Ar–H), 6.69 (ddd, J = 7.3, 7.3 and 1.0 Hz, 1H, Ar–H), 6.47
(d, J = 7.8 Hz, 1H, Ar–H), 3.33 (d, J = 8.8 Hz, 1H, NCH
A B A B
H ), 2.97 (d, J = 8.8 Hz, 1H, NCH H ), 2.74
(
s, 3H, CH ), 2.37 (dq, J = 16.4 and 2.8 Hz, 1H), 2.36 (dq, J = 16.4 and 2.8 Hz, 1H), 1.81 (t, J = 2.8
3
1
3
Hz, 3H), 1.40 (s, 3H, CH ) ppm. C NMR (CDCl , 100 MHz): δ=152.2 (s, Ar–C), 137.0 (s, Ar–C),
3
3
127.9 (d, Ar–CH), 122.2 (d, Ar–CH), 117.6 (d, Ar–CH), 107.3 (d, Ar–CH), 77.1 (s, C≡C), 76.0 (s,

ACCEPTED MANUSCRIPT
C≡C), 67.8 (t, CH ), 43.5 (s, C), 35.8 (q, CH ), 30.1 (t, CH ), 23.9 (q, CH ), 3.5 (q, CH ) ppm. HR-MS
2
3
2
3
3
+
+
(
ESI+) m/z calculated for [C H N] =[M+H] : 200.1434; found 200.1436.
14 18
1,3-Dimethyl-3-pent-2-ynylindoline (6ac): GP was carried out with 2-iodo-N-methyl-N-(2-
methylallyl)aniline 3a (71.7 mg, 0.25 mmol), pent-2-ynoic acid 2c (37 mg, 0.37 mmol),
Pd (dba) (2.28 mg, 1 mol%), TBAB (80.5 mg, 0.25 mmol), K CO (103.9 mg, 0.75 mmol) water
2
3
2
3
(
0.5 mL), under microwave irradiation (100 °C, 10 min, 300 W, closed vessel). Purification of the
crude material by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to
5:5) furnished the indoline 6ac (45.5 mg, 86%) as a light yellow oily compound, [TLC control
petroleum ether/ethyl acetate 100:0), R (3a)=0.8, R (6ac)=0.7, UV detection]. IR (MIR-ATR,
9
(
f
f
-
1
4
000–600 cm ): νmax=2956, 2914, 2858, 2806, 1605, 1489, 1454, 1375, 1298, 1245, 1214, 1156,
-1 1
1
110, 1020, 965, 741 cm . H NMR (CDCl , 400 MHz): δ=7.10 (ddd, J = 7.7, 7.7 and 1.2 Hz, 1H,
3
Ar–H), 7.06 (dd, J = 7.7 and 1.0 Hz, 1H, Ar–H), 6.68 (ddd, J = 7.7, 7.7 and 1.2 Hz, 1H, Ar–H), 6.47
(
d, J = 7.7 Hz, 1H, Ar–H), 3.33 (d, J = 8.8 Hz, 1H, NCH
s, 3H, CH ), 2.38 (dq, J = 16.1 and 2.0 Hz, 1H), 2.37 (dq, J = 16.1 and 2.0 Hz, 1H), 2.23–2.13 (m,
H, CH ), 1.40 (s, 3H, CH ), 1.13 (t, J = 7.6 Hz, 3H, CH ) ppm. C NMR (CDCl , 100 MHz): δ=152.2
A B A B
H ), 2.97 (d, J = 8.8 Hz, 1H, NCH H ), 2.74
(
3
1
3
2
2
3
3
3
(s, Ar–C), 137.0 (s, Ar–C), 127.9 (d, Ar–CH), 122.2 (d, Ar–CH), 117.6 (d, Ar–CH), 107.3 (d, Ar–CH),
8
3.4 (s, C≡C), 76.9 (s, C≡C), 67.9 (t, CH ), 43.5 (s, C), 35.8 (q, CH ), 30.2 (t, CH ), 23.9 (q, CH ),
2
3
2
3
+
+
1
4.3 (q, CH ), 12.4 (t, CH ) ppm. HR-MS (ESI+) m/z calculated for [C H N] =[M+H] : 214.1590;
3
2
15 20
found 214.1589.
3
-Hex-2-ynyl-1,3-dimethylindoline (6ad): GP was carried out with 2-iodo-N-methyl-N-(2-
methylallyl)aniline 3a (71.7 mg, 0.25 mmol), hex-2-ynoic acid 2d (42 mg, 0.37 mmol), Pd (dba)
2.28 mg, 1 mol%), TBAB (80.5 mg, 0.25 mmol), K CO (103.9 mg, 0.75 mmol) water (0.5 mL),
2
3
(
2
3
under microwave irradiation (100 °C, 10 min, 300 W, closed vessel). Purification of the crude
material by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 95:5)
furnished the indoline 6ad (47.6 mg, 85%) as a light yellow oily compound, [TLC control
(
petroleum ether/ethyl acetate 100:0), R (3a)=0.8, R (6ad)=0.7, UV detection]. IR (MIR-ATR,
f f
-
1
4
000–600 cm ): νmax=2956, 2866, 2807, 1605, 1487, 1455, 1376, 1250, 1155, 1109, 1020, 968,
-
1 1
7
42 cm . H NMR (CDCl , 400 MHz): δ=7.11 (ddd, J = 7.7, 7.7 and 1.2 Hz, 1H, Ar–H), 7.07 (dd, J =
3

ACCEPTED MANUSCRIPT
7.3 and 1.0 Hz, 1H, Ar–H), 6.69 (ddd, J = 7.7, 7.7 and 1.2 Hz, 1H, Ar–H), 6.48 (d, J = 7.8 Hz, 1H,
Ar–H), 3.35 (d, J = 8.8 Hz, 1H, NCH
A
H
B
), 2.99 (d, J = 8.8 Hz, 1H, NCH
A
H
B
), 2.75 (s, 3H, CH
3
), 2.41
(
(
dq, J = 16.1 and 2.1 Hz, 1H), 2.40 (dq, J = 16.1 and 2.1 Hz, 1H), 2.21–2.12 (m, 2H, CH
2
), 1.55
1
3
3 3 3
sext, J = 7.3 Hz, 2H), 1.43 (s, 3H, CH ), 1.00 (t, J = 7.3 Hz, 3H, CH ) ppm. C NMR (CDCl , 100
MHz): δ=152.2 (s, Ar–C), 136.9 (s, Ar–C), 127.9 (d, Ar–CH), 122.2 (d, Ar–CH), 117.7 (d, Ar–CH),
1
07.3 (d, Ar–CH), 81.8 (s, C≡C), 77.7 (s, C≡C), 67.8 (t, CH ), 43.5 (s, C), 35.8 (q, CH ), 30.2 (t, CH ),
2
3
2
2
4.0 (q, CH ), 22.5 (t, CH ), 20.8 (t, CH ), 13.5 (q, CH ) ppm. HR-MS (ESI+) m/z calculated for
3
2
2
3
+
+
[
C H N] =[M+H] : 228.1747; found 228.1736.
1
6 22
1-Ethyl-3-hex-2-ynyl-3-methylindoline (6bd): GP was carried out with 2-iodo-N-ethyl-2-iodo-
N-(2-methylallyl)aniline 3b (75.2 mg, 0.25 mmol), hex-2-ynoic acid 2d (42 mg, 0.37 mmol),
Pd (dba) (2.28 mg, 1 mol%), TBAB (80.5 mg, 0.25 mmol), K CO (103.9 mg, 0.75 mmol) water
0.5 mL), under microwave irradiation (100 °C, 10 min, 300 W, closed vessel). Purification of the
crude material by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to
7:3) furnished the indoline 6bd (49.2 mg, 82%) as a light yellow oily compound, [TLC control
petroleum ether/ethyl acetate 100:0), R (3b)=0.8, R (6bd)=0.7, UV detection]. IR (MIR-ATR,
2
3
2
3
(
9
(
f
f
-
1
4
000–600 cm ): νmax=2961, 2872, 2820, 1604, 1483, 1457, 1377, 1325, 1268, 1191, 1020, 740
-
1 1
cm . H NMR (CDCl , 400 MHz): δ=7.10 (ddd, J = 7.6, 7.6 and 1.5 Hz, 1H, Ar–H), 7.07 (dd, J = 7.3
3
and 1.5 Hz, 1H, Ar–H), 6.67 (dd, J = 7.3 and 7.3 Hz, 1H, Ar–H), 6.48 (d, J = 7.6 Hz, 1H, Ar–H), 3.38
(
d, J = 8.8 Hz, 1H, NCH H ), 3.26–3.06 (m, 2H), 3.04 (d, J = 8.8 Hz, 1H, NCH H ), 2.43 (dq, J = 16.1
A B A B
and 2.0 Hz, 1H), 2.40 (dq, J = 16.1 and 2.0 Hz, 1H), 2.22–2.13 (m, 2H, CH ), 1.53 (sext, J = 7.3 Hz,
2
1
3
2H), 1.43 (s, 3H, CH
3 3
), 1.18 (t, J = 7.1 Hz, 3H), 1.00 (t, J = 7.3 Hz, 3H) ppm. C NMR (CDCl , 100
MHz): δ=151.0 (s, Ar–C), 136.9 (s, Ar–C), 127.8 (d, Ar–CH), 122.3 (d, Ar–CH), 117.2 (d, Ar–CH),
1
07.1 (d, Ar–CH), 81.8 (s, C≡C), 77.7 (s, C≡C), 64.1 (t, CH
2
2 2
), 43.2 (s, C), 42.5 (t, CH ), 30.4 (t, CH ),
2
4.2 (q, CH
3
2
), 22.5 (t, CH ), 20.8 (t, CH
2
), 13.5 (q, CH
3
), 11.7 (q, CH ) ppm. HR-MS (ESI+) m/z
3
+
+
calculated for [C H N] =[M+H] : 242.1903; found 242.1886.
1
7 24
1-Benzyl-3-methyl-3-(3-phenylprop-2-ynyl)indoline (6ca): GP was carried out with N-benzyl-
N-(2-iodophenyl)-N-(2-methylprop-2-enyl)amine 3c (90.7 mg, 0.25 mmol), 3-phenylprop-2-
ynoic acid 2a (54.7 mg, 0.37 mmol), Pd (dba) (2.28 mg, 1 mol%), TBAB (80.5 mg, 0.25 mmol),
2
3

ACCEPTED MANUSCRIPT
K CO (103.9 mg, 0.75 mmol) water (0.5 mL), under microwave irradiation (100 °C, 10 min, 300
2
3
W, closed vessel). Purification of the crude material by silica gel column chromatography
petroleum ether/ethyl acetate, 100:0 to 93:7) furnished the indoline 6ca (76.3 mg, 92%) as a
light yellow oily compound, [TLC control (petroleum ether/ethyl acetate 100:0), R (3c)=0.7,
max=2965, 2922, 2817, , 1602, 1485,
378, 1316, 1266, 1189, 1072, 1022, 914, 745, 694 cm . H NMR (CDCl , 400 MHz): δ=7.43–7.24
m, 10H, Ar–H), 7.20 (d, J = 7.3 Hz, 1H, Ar–H), 7.13 (dd, J = 7.3 and 7.3 Hz, 1H, Ar–H), 6.75 (dd, J
(
f
-
1
f
R (6ca)=0.6, UV detection]. IR (MIR-ATR, 4000–600 cm ): ν
-
1 1
1
3
(
=
4
7.3 and 7.3 Hz, 1H, Ar–H), 6.54 (d, J = 7.8 Hz, 1H, Ar–H), 4.40 (d, J = 15.2 Hz ,1H, N–CH H –Ar),
A B
.24 (d, J = 15.2 Hz ,1H, N–CH H –Ar), 3.45 (d, J = 8.8 Hz ,1H, NCH H ), 3.13 (d, J = 8.8 Hz ,1H,
A
B
A B
1
3
NCH H ), 2.71 (dd, J = 17.1 and 1.5 Hz, 2H, CH ), 1.53 (s, 3H, CH ) ppm. C NMR (CDCl , 100
A
B
2
3
3
MHz): δ=151.1 (s, Ar–C), 138.3 (s, Ar–C), 136.3 (s, Ar–C), 131.6 (d, 2 × Ar–CH), 128.5 (d, 2 × Ar–
CH), 128.2 (d, 2 × Ar–CH), 128.0 (d, Ar–CH), 127.7 (d, 2 × Ar–CH), 127.5 (d, Ar–CH), 127.1 (d, Ar–
CH), 123.8 (s, Ar–C), 122.6 (d, Ar–CH), 117.7 (d, Ar–CH), 107.1 (d, Ar–CH), 87.7 (s, C≡C), 82.2 (s,
C≡C), 65.6 (t, CH ), 52.8 (t, CH ), 43.6 (s, C), 31.0 (t, CH ), 24.2 (q, CH ) ppm. HR-MS (ESI+) m/z
2
2
2
3
+
+
calculated for [C25H24N] =[M+H] : 338.1903; found 338.1910.
1-Benzyl-3-but-2-ynyl-3-methylindoline (6cb): GP was carried out with N-benzyl-N-(2-
iodophenyl)-N-(2-methylprop-2-enyl)amine 3c (90.7 mg, 0.25 mmol), but-2-ynoic acid 2b (32
mg, 0.37 mmol), Pd (dba) (2.28 mg, 1 mol%), TBAB (80.5 mg, 0.25 mmol), K CO (103.9 mg,
2
3
2
3
0.75 mmol) water (0.5 mL), under microwave irradiation (100 °C, 10 min, 300 W, closed vessel).
Purification of the crude material by silica gel column chromatography (petroleum ether/ethyl
acetate, 100:0 to 99:1) furnished the indoline 6cb (59.8 mg, 88%) as a light yellow oily
compound, [TLC control (petroleum ether/ethyl acetate 100:0), R (3c)=0.9, R (6cb)=0.8, UV
f
f
-
1
detection]. IR (MIR-ATR, 4000–600 cm ): νmax=2956, 2868, 2808, 1605, 1487, 1457, 1375, 1292,
-
1 1
1
7
4
1
1
157, 1110, 1022, 970, 744 cm . H NMR (CDCl
.02 (m, 2H, Ar–H), 6.69 (ddd, J = 7.3, 7.3 and 1.0 Hz, 1H, Ar–H), 6.48 (d, J = 7.3 Hz, 1H, Ar–H),
.33 (d, J = 15.2 Hz, 1H, N–CH –Ar), 4.22 (d, J = 15.2 Hz, 1H, N–CH –Ar), 3.34 (d, J = 8.8 Hz,
H, NCH ), 3.05 (d, J = 8.8 Hz, 1H, NCH ), 2.41 (dq, J = 16.4 and 2.4 Hz, 1H), 2.40 (dq, J =
6.4 and 2.4 Hz, 1H), 1.78 (t, J = 2.4 Hz, 3H, CH ), 1.40 (s, 3H, CH ) ppm. C NMR (CDCl , 100
3
, 400 MHz): δ=7.40–7.23 (m, 5H, Ar–H), 7.13–
A
H
B
A B
H
A
H
B
A B
H
1
3
3
3
3
MHz): δ=151.3 (s, Ar–C), 138.5 (s, Ar–C), 136.6 (s, Ar–C), 128.5 (d, 2 × Ar–CH), 127.9 (d, Ar–CH),

ACCEPTED MANUSCRIPT
127.6 (d, 2 × Ar–CH), 127.0 (d, Ar–CH), 122.4 (d, Ar–CH), 117.5 (d, Ar–CH), 107.0 (d, Ar–CH),
7
7.1 (s, C≡C), 76.5 (s, C≡C), 65.5 (t, CH ), 52.8 (t, CH ), 43.4 (s, C), 30.4 (t, CH ), 24.3 (q, CH ), 3.5
2
2
2
3
+
+
(
q, CH
3
) ppm. HR-MS (ESI+) m/z calculated for [C20H22N] =[M+H] : 276.1747; found 276.1749.
1-Benzyl-3-methyl-3-pent-2-ynylindoline (6cc): GP was carried out with N-benzyl-N-(2-
iodophenyl)-N-(2-methylprop-2-enyl)amine 3c (90.7 mg, 0.25 mmol), pent-2-ynoic acid 2c (37
mg, 0.37 mmol), Pd (dba) (2.28 mg, 1 mol%), TBAB (80.5 mg, 0.25 mmol), K CO (103.9 mg,
2
3
2
3
0.75 mmol) water (0.5 mL), under microwave irradiation (100 °C, 10 min, 300 W, closed vessel).
Purification of the crude material by silica gel column chromatography (petroleum ether/ethyl
acetate, 100:0 to 99:1) furnished the indoline 6cc (60.3 mg, 85%) as a light yellow oily
compound, [TLC control (petroleum ether/ethyl acetate 100:0), R (3c)=0.9, R (6cc)=0.8, UV
f
f
-
1
detection]. IR (MIR-ATR, 4000–600 cm ): νmax=2959, 2915, 2821, 1602, 1487, 1452, 1362, 1249,
-
1 1
1
155, 1025, 945, 736, 698, cm . H NMR (CDCl
3
, 400 MHz): δ=7.39–7.27 (m, 4H, Ar–H), 7.30–
7.23 (m, 1H, Ar–H), 7.11 (d, J = 7.3 Hz, 1H, Ar–H), 7.09 (d, J = 8.8 and 1.0 Hz, 1H, Ar–H), 6.70 (dd,
J = 7.8 and 7.8 Hz, 1H, Ar–H), 6.48 (d, J = 7.8 Hz, 1H, Ar–H), 4.34 (d, J = 15.2 Hz, 1H, N–CH
A B
H –
Ar), 4.22 (d, J = 15.2 Hz, 1H, N–CH H –Ar), 3.35 (d, J = 9.3 Hz, 1H, NCH H ), 3.05 (d, J = 9.3 Hz,
A
B
A B
1H, NCH H ), 2.43 (dq, J = 16.1 and 2.2 Hz, 1H), 2.42 (dq, J = 16.4 and 2.4 Hz, 1H), 2.21–2.11 (m,
A B
1
3
2
H, CH ), 1.42 (s, 3H, CH ), 1.11 (t, J = 7.6 Hz, 3H, CH ) ppm. C NMR (CDCl , 100 MHz): δ=151.3
2
3
3
3
(s, Ar–C), 138.5 (s, Ar–C), 136.6 (s, Ar–C), 128.5 (d, 2 × Ar–CH), 127.9 (d, Ar–CH), 127.6 (d, 2 ×
Ar–CH), 127.0 (d, Ar–CH), 122.5 (d, Ar–CH), 117.5 (d, Ar–CH), 107.0 (d, Ar–CH), 83.4 (s, C≡C),
7
1
2
6.8 (s, C≡C), 65.5 (t, CH ), 52.8 (t, CH ), 43.4 (s, C), 30.4 (t, CH ), 24.2 (q, CH ), 14.3 (q, CH ),
2
2
2
3
3
+
+
2.4 (t, CH ) ppm. HR-MS (ESI+) m/z calculated for [C H N] =[M+H] : 290.1903; found
2
21 24
90.1882.
-Benzyl-3-hex-2-ynyl-3-methylindoline (6cd): GP was carried out with N-benzyl-N-(2-
1
iodophenyl)-N-(2-methylprop-2-enyl)amine 3c (90.7 mg, 0.25 mmol), hex-2-ynoic acid 2d (42
mg, 0.37 mmol), Pd (dba) (2.28 mg, 1 mol%), TBAB (80.5 mg, 0.25 mmol), K CO (103.9 mg,
2
3
2
3
0.75 mmol) water (0.5 mL), under microwave irradiation (100 °C, 10 min, 300 W, closed vessel).
Purification of the crude material by silica gel column chromatography (petroleum ether/ethyl
acetate, 100:0 to 99:1) furnished the indoline 6cd (66.6 mg, 89%) as a light yellow oily

ACCEPTED MANUSCRIPT
compound, [TLC control (petroleum ether/ethyl acetate 100:0), R (3c)=0.9, R (6cd)=0.8, UV
f
f
-
1
detection]. IR (MIR-ATR, 4000–600 cm ): νmax=2959, 2920, 2825, 1604, 1488, 1454, 1362, 1237,
-
1 1
1
155, 1028, 736, 700, 682 cm . H NMR (CDCl
J = 7.8 and 1.0 Hz, 1H, Ar–H), 7.07 (ddd, J = 7.5, 7.5 and 1.3 Hz, 1H, Ar–H), 6.70 (ddd, J = 7.5, 7.5
and 1.0 Hz, 1H, Ar–H), 6.48 (d, J = 7.8 Hz, 1H, Ar–H), 4.33 (d, J = 15.2 Hz, 1H, N–CH –Ar), 4.21
d, J = 15.2 Hz, 1H, N–CH H –Ar), 3.35 (d, J = 8.8 Hz, 1H, NCH H ), 3.04 (d, J = 8.8 Hz, 1H,
3
, 400 MHz): δ=7.38–7.23 (m, 5H, Ar–H), 7.10 (dd,
A B
H
(
A
B
A B
NCH H ), 2.43 (dq, J = 16.1 and 2.2 Hz, 1H), 2.42 (dq, J = 16.4 and 2.4 Hz, 1H), 2.17–2.08 (m, 2H,
A
B
1
3
CH ), 1.46 (sext, J = 7.3 Hz, 2H, CH ), 1.42 (s, 3H, CH ), 0.95 (t, J = 7.3 Hz, 3H, CH ) ppm. C NMR
2
2
3
3
(
CDCl , 100 MHz): δ=151.2 (s, Ar–C), 138.5 (s, Ar–C), 136.6 (s, Ar–C), 128.5 (d, 2 × Ar–CH), 127.9
3
(d, Ar–CH), 127.7 (d, 2 × Ar–CH), 127.0 (d, Ar–CH), 122.5 (d, Ar–CH), 117.6 (d, Ar–CH), 107.0 (d,
Ar–CH), 81.9 (s, C≡C), 77.6 (s, C≡C), 65.6 (t, CH ), 52.9 (t, CH ), 43.5 (s, C), 30.5 (t, CH ), 24.3 (q,
2
2
2
CH ), 22.5 (t, CH ), 20.8 (t, CH ), 13.5 (q, CH ) ppm. HR-MS (ESI+) m/z calculated for
3
2
2
3
+
+
[
22
C H26N] =[M+H] : 304.2060; found 304.2063.
3-But-2-ynyl-1,3-dimethyl-1,3-dihydro-2H-indol-2-one (7ab): GP was carried out with N-(2-
iodophenyl)-N,2-dimethylacrylamide 4a (75 mg, 0.25 mmol), but-2-ynoic acid 2b (32 mg, 0.37
mmol), Pd (dba) (2.28 mg, 1 mol%), TBAB (80.5 mg, 0.25 mmol), K CO (103.9 mg, 0.75 mmol)
2
3
2
3
water (0.5 mL), under microwave irradiation (100 °C, 10 min, 300 W, closed vessel). Purification
of the crude material by silica gel column chromatography (petroleum ether/ethyl acetate,
100:0 to 90:10) furnished the dihydrobenzofuran 7ab (47.7 mg, 90%) as a light yellow oily
compound, [TLC control (petroleum ether/ethyl acetate 92:8), R (4a)=0.6, R (7ab)=0.5, UV
f
f
-
1
detection]. IR (MIR-ATR, 4000–600 cm ): νmax=2966, 2924, 1710, 1612, 1462, 1371, 1251, 1186,
-
1 1
1
103, 754, 699 cm . H NMR (CDCl
3
, 400 MHz): δ=7.41 (dd, J = 7.3 and 1.0 Hz, 1H, Ar–H), 7.28
(ddd, J = 7.8, 7.8 and 1.5 Hz, 1H, Ar–H), 7.07 (ddd, J = 7.8, 7.8 and 1.5 Hz, 1H, Ar–H), 6.84 (d, J =
7.8 Hz, 1H, Ar–H), 3.20 (s, 3H), 2.63 (dq, J = 16.4 and 2.4 Hz, 1H), 2.40 (dq, J = 16.4 and 2.4 Hz,
1
3
1
H), 1.73 (t, J = 2.4 Hz, 3H), 1.42 (s, 3H, CH ) ppm. C NMR (CDCl , 100 MHz): δ=179.7 (s, N–
3
3
CO), 142.9 (s, Ar–C), 133.5 (s, Ar–C), 128.0 (d, Ar–CH), 123.2 (d, Ar–CH), 122.4 (d, Ar–CH), 107.8
(
d, Ar–CH), 78.0 (s, C≡C), 74.3 (s, C≡C), 47.0 (s, C), 28.1 (t, CH ), 26.2 (q, CH ), 21.6 (q, CH ), 3.4
2
3
3
+
+
(
q, CH ) ppm. HR-MS (ESI+) m/z calculated for [C H NO] =[M+H] : 214.1226; found 214.1227.
3
14 16

ACCEPTED MANUSCRIPT
1,3-Dimethyl-3-pent-2-ynyl-1,3-dihydro-2H-indol-2-one (7ac): GP was carried out with N-(2-
iodophenyl)-N,2-dimethylacrylamide 4a (75 mg, 0.25 mmol), pent-2-ynoic acid 2c (37 mg, 0.37
mmol), Pd (dba) (2.28 mg, 1 mol%), TBAB (80.5 mg, 0.25 mmol), K CO (103.9 mg, 0.75 mmol)
2
3
2
3
water (0.5 mL), under microwave irradiation (100 °C, 10 min, 300 W, closed vessel). Purification
of the crude material by silica gel column chromatography (petroleum ether/ethyl acetate,
100:0 to 91:9) furnished the dihydrobenzofuran 7ac (49.2 mg, 88%) as a light yellow oily
compound, [TLC control (petroleum ether/ethyl acetate 92:8), R (4a)=0.8, R (7ac)=0.7, UV
f
f
-
1
detection]. IR (MIR-ATR, 4000–600 cm ): νmax=2962, 2926, 2871, 1708, 1609, 1455, 1355, 1174,
-
1 1
1
001, 742, 698, 636 cm . H NMR (CDCl , 400 MHz): δ=7.41 (dd, J = 7.3 and 1.0 Hz, 1H, Ar–H),
3
7.28 (ddd, J = 7.8, 7.8 and 1.5 Hz, 1H, Ar–H), 7.07 (ddd, J = 7.8, 7.8 and 1.5 Hz, 1H, Ar–H), 6.84
(d, J = 7.8 Hz, 1H, Ar–H), 3.20 (s, 3H), 2.63 (dt, J = 16.1 and 2.4 Hz, 1H), 2.43 (dt, J = 16.1 and 2.4
1
3
Hz, 1H), 2.13-2.03 (m, 2H), 1.44 (s, 3H, CH ), 1.02 (t, J = 7.3 Hz, 3H, CH ) ppm. C NMR (CDCl3,
3
3
1
00 MHz): δ=179.8 (s, N–CO), 143.1 (s, Ar–C), 133.5 (s, Ar–C), 127.9 (d, Ar–CH), 123.2 (d, Ar–
CH), 122.4 (d, Ar–CH), 107.8 (d, Ar–CH), 84.1 (s, C≡C), 74.7 (s, C≡C), 47.1 (s, C), 28.3 (t, CH ),
) ppm. HR-MS (ESI+) m/z calculated for
2
26.2 (q, CH
3
3 3 2
), 21.6 (q, CH ), 14.1 (q, CH ), 12.3 (t, CH
+
+
[
C
15
H
18NO] =[M+H] : 228.1383; found 228.1389.
3-Hex-2-ynyl-1,3-dimethyl-1,3-dihydro-2H-indol-2-one (7ad): GP was carried out with N-(2-
iodophenyl)-N,2-dimethylacrylamide 4a (75 mg, 0.25 mmol), hex-2-ynoic acid 2d (42 mg, 0.37
mmol), Pd (dba) (2.28 mg, 1 mol%), TBAB (80.5 mg, 0.25 mmol), K CO (103.9 mg, 0.75 mmol)
2
3
2
3
water (0.5 mL), under microwave irradiation (100 °C, 10 min, 300 W, closed vessel). Purification
of the crude material by silica gel column chromatography (petroleum ether/ethyl acetate,
1
00:0 to 89:11) furnished the dihydrobenzofuran 7ad (51.6 mg, 86%) as a light yellow oily
compound, [TLC control (petroleum ether/ethyl acetate 92:8), R (4a)=0.7, R (7ad)=0.6, UV
max=2962, 2927, 2871, 1709, 1610, 1456, 1355, 1174,
080, 1001, 927, 739, 697, 635 cm . H NMR (CDCl , 400 MHz): δ=7.39 (dd, J = 7.3 and 1.0 Hz,
H, Ar–H), 7.28 (ddd, J = 7.8, 7.8 and 1.5 Hz, 1H, Ar–H), 7.07 (ddd, J = 7.8, 7.8 and 1.5 Hz, 1H,
f
f
-
1
detection]. IR (MIR-ATR, 4000–600 cm ):
ν
-
1 1
1
1
3
Ar–H), 6.84 (d, J = 7.8 Hz, 1H, Ar–H), 3.21 (s, 3H), 2.65 (dt, J = 16.1 and 2.5 Hz, 1H), 2.46 (dt, J =
16.1 and 2.5 Hz, 1H), 2.09-2.00 (m, 2H), 1.43 (s, 3H, CH ), 1.38 (sext, J = 7.3 Hz, 2H), 0.85 (t, J =
3
1
3
7
.3 Hz, 3H, CH ) ppm. C NMR (CDCl , 100 MHz): δ=179.7 (s, N–CO), 143.1 (s, Ar–C), 133.5 (s,
3
3

ACCEPTED MANUSCRIPT
Ar–C), 127.9 (d, Ar–CH), 123.1 (d, Ar–CH), 122.4 (d, Ar–CH), 107.8 (d, Ar–CH), 82.5 (s, C≡C), 75.4
(
s, C≡C), 47.2 (s, C), 28.2 (t, CH ), 26.2 (q, CH ), 22.2 (t, CH ), 21.7 (q, CH ), 20.6 (t, CH ), 13.3 (q,
2
3
2
3
2
+
+
CH ) ppm. HR-MS (ESI+) m/z calculated for [C H NO] =[M+H] : 242.1539; found 242.1539.
3
16 20
1-Benzyl-3-but-2-ynyl-3-methyl-1,3-dihydro-2H-indol-2-one (7bb): GP was carried out with
N-benzyl-N-(2-iodophenyl)-2-methylacrylamide 4b (94 mg, 0.25 mmol), but-2-ynoic acid 2b (32
mg, 0.37 mmol), Pd (dba) (2.28 mg, 1 mol%), TBAB (80.5 mg, 0.25 mmol), K CO (103.9 mg,
2
3
2
3
0.75 mmol) water (0.5 mL), under microwave irradiation (100 °C, 10 min, 300 W, closed vessel).
Purification of the crude material by silica gel column chromatography (petroleum ether/ethyl
acetate, 100:0 to 86:14) furnished the dihydrobenzofuran 7bb (63.3 mg, 88%) as a light yellow
oily compound, [TLC control (petroleum ether/ethyl acetate 92:8), R (4b)=0.8, R (7bb)=0.7, UV
f
f
-
1
detection]. IR (MIR-ATR, 4000–600 cm ): νmax=2921, 2853, 1709, 1606, 1501, 1455, 1357, 1290,
-1 1
1
245, 1173, 1103, 1029, 831, 743, 698, 642 cm . H NMR (CDCl , 400 MHz): δ=7.36 (dd, J = 7.3
3
and 1.0 Hz, 1H, Ar–H), 7.34–7.20 (m, 5H, Ar–H), 7.15 (ddd, J = 7.8, 7.8 and 1.5 Hz, 1H, Ar–H),
7
.03 (ddd, J = 7.8, 7.8 and 1.5 Hz, 1H, Ar–H), 6.70 (d, J = 7.8 Hz, 1H, Ar–H), 5.08 (d, J = 15.6 Hz,
H, N–CH –Ar), 4.76 (d, J = 15.6 Hz, 1H, N–CH –Ar), 2.69 (dq, J = 16.1 and 2.4 Hz, 1H), 2.57
1
A
H
B
A B
H
1
3
(
dq, J = 16.1 and 2.4 Hz, 1H), 1.66 (t, J = 2.4 Hz, 3H), 1.46 (s, 3H, CH ) ppm. C NMR (CDCl , 100
3 3
MHz): δ=179.8 (s, N–CO), 142.2 (s, Ar–C), 135.9 (s, Ar–C), 133.4 (s, Ar–C), 128.7 (d, 2 × Ar–CH),
1
1
3
2
27.8 (d, Ar–CH), 127.4 (d, Ar–CH), 127.2 (d, 2 × Ar–CH), 123.0 (d, Ar–CH), 122.4 (d, Ar–CH),
08.9 (d, Ar–CH), 77.9 (s, C≡C), 74.4 (s, C≡C), 47.3 (s, C), 43.6 (t, CH ), 28.2 (t, CH ), 22.4 (q, CH ),
2
2
3
+
+
.4 (q, CH ) ppm. HR-MS (ESI+) m/z calculated for [C H NO] =[M+H] : 290.1539; found
3
20 20
90.1550.
-Benzyl-3-methyl-3-pent-2-ynyl-1,3-dihydro-2H-indol-2-one (7bc): GP was carried out with
1
N-benzyl-N-(2-iodophenyl)-2-methylacrylamide 4b (94 mg, 0.25 mmol), pent-2-ynoic acid 2c (37
mg, 0.37 mmol), Pd (dba) (2.28 mg, 1 mol%), TBAB (80.5 mg, 0.25 mmol), K CO (103.9 mg,
2
3
2
3
0.75 mmol) water (0.5 mL), under microwave irradiation (100 °C, 10 min, 300 W, closed vessel).
Purification of the crude material by silica gel column chromatography (petroleum ether/ethyl
acetate, 100:0 to 92:8) furnished the dihydrobenzofuran 7bc (66.7 mg, 89%) as a light yellow
oily compound, [TLC control (petroleum ether/ethyl acetate 92:8), R (4b)=0.9, R (7bc)=0.8, UV
f
f

ACCEPTED MANUSCRIPT
-
1
detection]. IR (MIR-ATR, 4000–600 cm ): νmax=2968, 2923, 1707, 1608, 1466, 1359, 1174, 1106,
-
1 1
1
7
1
=
2
022, 923, 747, 695 cm . H NMR (CDCl , 400 MHz): δ=7.38 (dd, J = 7.3 and 1.0 Hz, 1H, Ar–H),
3
.35–7.20 (m, 5H, Ar–H), 7.15 (ddd, J = 7.3, 7.3 and 1.5 Hz, 1H, Ar–H), 7.03 (ddd, J = 7.3, 7.3 and
.5 Hz, 1H, Ar–H), 6.71 (d, J = 7.8 Hz, 1H, Ar–H), 5.02 (d, J = 15.6 Hz, 1H, N–CH
15.6 Hz, 1H, N–CH –Ar), 2.70 (dt, J = 16.6 and 2.4 Hz, 1H), 2.57 (dt, J = 16.6 and 2.4 Hz, 1H),
.07-2.01 (m, 2H), 1.47 (s, 3H, CH ), 0.95 (t, J = 7.3 Hz, 3H, CH ) ppm. C NMR (CDCl , 100 MHz):
A B
H –Ar), 4.80 (d, J
A B
H
1
3
3
3
3
δ=179.9 (s, N–CO), 142.2 (s, Ar–C), 136.0 (s, Ar–C), 133.5 (s, Ar–C), 128.7 (d, 2 × Ar–CH), 127.8
d, Ar–CH), 127.5 (d, Ar–CH), 127.2 (d, 2 × Ar–CH), 123.2 (d, Ar–CH), 122.4 (d, Ar–CH), 108.9 (d,
Ar–CH), 84.1 (s, C≡C), 74.7 (s, C≡C), 47.3 (s, C), 43.6 (t, CH ), 28.2 (t, CH ), 22.2 (q, CH ), 13.9 (q,
(
2
2
3
+
+
CH ), 12.3 (t, CH ) ppm. HR-MS (ESI+) m/z calculated for [C H NO] =[M+H] : 304.1696; found
3
2
21 22
304.1675.
1-Benzyl-3-hex-2-ynyl-3-methyl-1,3-dihydro-2H-indol-2-one (7bd): GP was carried out with
N-benzyl-N-(2-iodophenyl)-2-methylacrylamide 4b (94 mg, 0.25 mmol), hex-2-ynoic acid 2d (42
mg, 0.37 mmol), Pd (dba) (2.28 mg, 1 mol%), TBAB (80.5 mg, 0.25 mmol), K CO (103.9 mg,
2
3
2
3
0.75 mmol) water (0.5 mL), under microwave irradiation (100 °C, 10 min, 300 W, closed vessel).
Purification of the crude material by silica gel column chromatography (petroleum ether/ethyl
acetate, 100:0 to 90:10) furnished the dihydrobenzofuran 7bd (63.2 mg, 80%) as a light yellow
oily compound, [TLC control (petroleum ether/ethyl acetate 92:8), R (4b)=0.8, R (7bd)=0.7, UV
f
f
-
1
detection]. IR (MIR-ATR, 4000–600 cm ): νmax=2970, 2924, 1710, 1609, 1485, 1446, 1355, 1267,
-
1 1
1
1
7
176, 999, 872, 786, 747, 694 cm . H NMR (CDCl , 400 MHz): δ=7.37 (dd, J = 7.3 and 1.0 Hz,
3
H, Ar–H), 7.34–7.20 (m, 5H, Ar–H), 7.14 (ddd, J = 7.8, 7.8 and 1.5 Hz, 1H, Ar–H), 7.02 (ddd, J =
.8, 7.8 and 1.5 Hz, 1H, Ar–H), 6.71 (d, J = 7.8 Hz, 1H, Ar–H), 5.00 (d, J = 15.6 Hz, 1H, N–CH
–Ar), 2.72 (dt, J = 16.1 and 2.4 Hz, 1H), 2.58 (dt, J = 16.1
and 2.4 Hz, 1H), 2.05-1.97 (m, 2H), 1.47 (s, 3H, CH ), 1.32 (sext, J = 7.3 Hz, 2H), 0.79 (t, J = 7.3
Hz, 3H, CH ) ppm. C NMR (CDCl , 100 MHz): δ=179.8 (s, N–CO), 142.2 (s, Ar–C), 136.0 (s, Ar–
A B
H –
A B
Ar), 4.82 (d, J = 15.6 Hz, 1H, N–CH H
3
1
3
3
3
C), 133.5 (s, Ar–C), 128.7 (d, 2 × Ar–CH), 127.8 (d, Ar–CH), 127.5 (d, Ar–CH), 127.2 (d, 2 × Ar–
CH), 123.2 (d, Ar–CH), 122.4 (d, Ar–CH), 108.9 (d, Ar–CH), 82.6 (s, C≡C), 75.4 (s, C≡C), 47.3 (s, C),
4
3.7 (t, CH ), 28.2 (t, CH ), 22.3 (q, CH ), 22.1 (t, CH ), 20.6 (t, CH ), 13.3 (q, CH ) ppm. HR-MS
2 2 3 2 2 3
+
+
(
ESI+) m/z calculated for [C H NO] =[M+H] : 318.1852; found 318.1832.
22 24