Synthesis of Functionalized Benzo[b]furans via Oxidative Cyclization of o-Cinnamyl Phenols

Article abstract of DOI:10.1021/acs.joc.6b02752

Disclosed herein is an efficient synthetic route for the synthesis of functionalized 2-benzyl benzo[b]furans via a regioselective 5-exo-trig intramolecular oxidative cyclization of ortho-cinnamyl phenols using [PdCl₂(CH₃CN)₂] as catalyst and benzoquinone as an oxidant. Further, a sequential ortho-cinnamylation of phenols using cinnamyl alcohols catalyzed by Re₂O₇, followed by an oxidative cyclization using the above Pd catalyst, is performed. The reaction showed broad substrate scope with good to excellent yields.

Full text of DOI:10.1021/acs.joc.6b02752

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Article
Synthesis of Functionalized Benzo[b]furans via
Oxidative Cyclization of o-Cinnamyl Phenols
Mohammad Rehan, Rajender Nallagonda, Braja Gopal Das, Tannu Meena, and Prasanta Ghorai
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b02752 • Publication Date (Web): 02 Mar 2017
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Synthesis of Functionalized Benzo[b]furans via Oxidative Cyclization
of o-Cinnamyl Phenols
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Mohammad Rehan, Rajender Nallagonda, Braja Gopal Das, Tannu Meena and Prasanta Ghorai*
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Department of Chemistry, Indian Institute of Science Education and Research Bhopal, Bhauri, Bhopal-
462066, India.
ABSTRACT: Disclosed herein an efficient synthetic route for the synthesis of functionalized 2-benzyl
benzo[b]furans via a regioselective 5-exo-trig intramolecular oxidative cyclization of ortho-cinnamyl
phenols using [PdCl2(CH3CN)2] as catalyst and benzoquinone as an oxidant. Further, a sequential ortho-
cinnamyaltion of phenols using cinnamyl alcohols catalyzed by Re2O7 followed by an oxidative cycliza-
tion using the above Pd-catalyst is performed. The reaction showed broad substrate scope with good to
excellent yields.
INTRODUCTION
Benzo[b]furan is a common structural motif found in natural products, pharmaceuticals and agrochemi-
cals.1 Derivatives of benzo[b]furans are acting, for examples, as antitumor2/anticancer-agents,3 5-
lipoxygenase4/mTOR signaling5a/angiotensin-inhibitors,5b and immunosuppressive activitors.6 The in-
triguing biological properties, medicinal applications and molecular architecture of benzo[b]furan based
natural products continue to draw a challenge and motivation for their synthesis. Various efficient syn-
thetic method has been developed;7 the traditional strategies for accessing the functionalized benzofu-
rans relied mainly on the transition-metal catalyzed inter- or intra-molecular heteroannulation of pre-
functionalized substrates (such as ortho-halo8 or ortho-alkynyl9 phenols). Recently, efforts have been
directed towards the synthesis of benzo[b]furans via ortho C–H activation/functionalization of phenols
(Scheme 1).10-15 Notably, highly substituted benzo[b]furan motifs are also present in various leading
drugs and organic materials. In particular, a significant number of natural products and synthetic com-
pounds contain the 2-benzyl 3-aryl/alkyl benzo[b]furan core (see Figure 1).16 Despite the significant ad-
vances in the synthesis of benzo[b]furans, selective synthesis of 2-benzyl 3-aryl/alkyl benzo[b]furan
motifs from readily accessible phenols still remains a daunting challenge. Notably, among the above
mentioned methods, only the ortho-propargylation/annulation strategy successfully provided such moie-
ty, albeit with limited substrate scope.13,17 Therefore, the development of a method to synthesize the
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above mentioned benzo[b]furans from readily available substrates with broad substrate scope would be
significantly rewarding.
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Figure 1. Bioactive 2-benzyl benzo[b]furans
Inspired by the oxidative-annulation strategy,18 our group has a long-standing interest in the Pd-
catalysed oxidative cycloannulation of various cinnamyl-substituted building blocks, which has been
proven to be an important strategy for the synthesis of many hetrocycles.19 For instances, o-
cinnamylanilines have been utilized for the synthesis of 2-benzyl indoles19a and 2-aryl quinolines19b.
More recently, the synthesis of 2-benzyl furans also have been developed from 2-cinnamyl-1,3-
dicarbonyls.19c Here, we sought for the synthesis of functionalized 2-benzyl 3-aryl/alkyl benzo[b]furan
via an intramolecular oxidative cyclization of o-cinnamylphenols.20
Ar
Previous reports:
Ar
R2
or
HO2C
R1
R2
R
Ar
(Ref.10)
R
R1
O
OH
O
[M]
(Ref.11)
R
O
CO2R2
Ar1
R1
HO
OH
(Ref.12)
R
(Ref.13)
Ar2
CO2R2
Ar1
Ar2
R
R1
R
O
Ar2
O
Ar1
This work:
FC ortho-cinnamylation/oxidative cycloisomerization
OC
FG
FC
FG
R
R
FG
R
Pd
HO
OH
Re
Ar
O2
O
OH
Ar
Ar
o-Cinnamylphenol
Pd
Re
one-pot
Scheme 1. Synthesis of Functionalized Benzo[b]furans from Phenol
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Further, a simple and effecient one-pot protocol for the synthesis of functionalized 2-benzyl
benzo[b]furan via a sequential o-cinnamylation of phenol followed by oxidative cyclization has also
been demonstrated. An easy avaiablility of the cinnamyl alcohols compared to the propargyl alcohol
might provide a broader synthetic utility of the current methodology.
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RESULTS AND DISCUSSION
The reaction optimization studies for the oxidative cyclization of the model substrate o-cinnamylphenol
(1a), which was prepared via a Friedel-Crafts alkylation of cinnamylalcohol with phenols using Re2O7
catalyst in acetonitrile as solvent (for details, see Supporting Information), is summarised in Table 1.
When 1a was stirred in 1,4-dioxane at 80 oC in the presence of a 5 mol% of various palladium catlysts
(such as Pd(OAc)2, [Pd(PPh3)2Cl2], Pd(OTFA)2, PdCl2 and [PdCl2(CH3CN)2], entries 1-5, respectively),
it was observed that [PdCl2(CH3CN)2] provided the desired 2-benzyl-5-methyl-3-phenyl benzo[b]furan
3a (entry 5) in 38% isolated yield in the presence of O2 ballon as an oxidant.
Table 1. Catalyst optimizationa
H3C
Ph
H3C
catalyst (5 mol %)
Oxidant
OH
O
Ph
Ph
Ph
80 o
C
3a
1a (0.2 mmol)
entry Catalyst
Oxidant
O2
Solvent
toluene
toluene
toluene
toluene
toluene
toluene
1,4-dioxane
Yield (%)b
1
2
3
4
5
6
7
8
Pd(OAc)2
28
Pd(PPh3)2Cl2
Pd(OTFA)2
O2
trace
17
O2
PdCl2
O2
23
PdCl2(CH3CN)2
PdCl2(CH3CN)2
PdCl2(CH3CN)2
PdCl2(CH3CN)2
O2
38
BQ
BQ
BQ
66
85
Other solventsc <47
aReaction conditions: o-Cinnamylphenol 1 (0.20 mmol), PdCl2(CH3CN)2 (5 mol %), BQ (1 equiv), 1,4-
b
c
dioxane (1.0 mL), 5 h. Isolated yields after column chromatography. Other solvents such as DCE,
MeCN, THF and Et2O.
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When the same reaction was carried out in presence of benzoquinone (BQ) as oxidant instead of oxygen,
the yield of the product was substantially increased (entry 6). Screening of the solvents such as THF,
DCE, CH3CN, 1,4-dioxane, toluene and diethyl ether, the reactivity in 1,4-dioxane was found to be the
best using [PdCl2(CH3CN)2] as catalyst and BQ as oxidant (entry 7). This reactivity could be because of
the better solubility of all the reaction components.
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After establishing the efficient reaction conditions for the intramolecular catalytic oxidative cyclization
reaction, the substrate scope was studied (Scheme 2). The overall process was shown to be effective in
the presence of various substituted o-cinnamylphenols (1a-q). Substrates with electron-donating substi-
tutents, such as Me- (3a), MeO- (3b), tert-butyl- (3c), BnO- (3d) and Ph- (3e), groups on the phenol
moiety, reacted nicely to provide the desired 2-benzyl benzo[b]furans in good to excellent yields.
Similarly, substrates with electron-withdrawing substituents, including, NC- (3f), O2N- (3g), F- (3h), Cl-
(3i, 3l-n and 3q), Br- (3j, 3m and 3o) and I- (3k) yielded the corresponding 2-benzyl benzo[b]furans
smoothly. Remarkably, halogen substitutions on phenol substrate such as iodo, bromo and chloro, which
Scheme 2. Variation of aryl phenola
aReaction conditions: o-Cinnamylphenol 1 (0.20 mmol), PdCl2(CH3CN)2 (5 mol %), BQ (1 equiv), 1,4-
dioxane (1 mL). bIsolated yields after column chromatography.
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are sensitive to palladium-catalysed reactions, were also successfully converted to the desired function-
alized benzo[b]furans without any complication. Notably, di- (3l-s) and tri-(3t)-substituted o-
cinnamylphenols were also tolerated well in the current reaction conditions. Di-substituted functional
groups such as hydroxyl (3u) and amide (3v) were also tolerated under these reaction conditions. The
structure of the compound 3a was confirmed by X-ray crystallographic analysis.
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Scheme 3. Variation of allyl counterparta,b
aReaction conditions: o-Cinnamylphenol 2 (0.20 mmol), PdCl2(CH3CN)2 (5 mol %), BQ (1 equiv), 1,4-
dioxane (1 mL). bIsolated yields.
To further expand the substrate scope, a variety of o-cinnamylphenols were examined under the current
oxidative cyclisation reaction conditions, which are summerized in Scheme 3. Various symmetrical
substitutions were tolerated on 1′,3′-diarylallyls attached to phenols at the ortho-position to provide
good yields of the corresponding benzo[b]furans. Substituents such as p-methyl (5a), p-fluoro (5b), p-
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chloro (5c), p-bromo (5d) and p-biphenyl (5e) worked smoothly to provide the desired benzo[b]furan. A
similar reactivity was observed with o-cinnamylphenol having α-naphthyl (5f) and 2-thiophenyl- (5g) as
the aryl counterpart on the cinnamyl moiety. The unsymmetrically substituted o-cinnamylphenols were
also easily underwent cycloannulation to afford the benzo[b]furans (5h-r) with good yields. 3-
Unsubstituted (5h-i, 5p) as well as alkyl substitutions at 3-position such as methyl (5j-n, 5q) and
cyclohexyl (5o) groups on 2-benzyl benzo[b]furans were also synthesized using this methodology. Even,
heteroaromatic rings, such as 2-thiophenyl (5g), 2-furyl (5l), pyrole (5m) and indole (5n) remained
effective under these conditions. 2-allyl substituted phenols were also tolerated under the same reaction
conditions and provided the corresponding (5s) and (5t) benzo[b]furan with good yields.
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Scheme 4. Synthesis of Melatonin Receptor Ligand
Scheme 5. Synthesis of Anti-tumor and Hypocholesterolemic Agent
Scheme 6. Synthesis of Inhibitor of the Akt/mTOR
To illustrate the practical synthetic utility of our methodology, the synthesis of the melatonin receptor
ligand A16a (Scheme 4), the anti-tumor/hypocholesterolemic agent B (Scheme 5) and the Akt/mtor
signaling inhibitor C (Scheme 6), has been realized from correponding 2-benzyl benzo[b]furans 5q, 5r
and 5i, respectively.
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To showcase the scalability and the practicality of the process, we performed a gram-scale reaction of 1a
to provide the desired benzo[b]furan 3a as shown in Scheme 7.
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Scheme 7. Gram Scale Synthesis
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Further, a simple sequential reaction protocol has been developed for the synthesis of functionalized 2-
benzyl benzo[b]furans via Friedel-Crafts alkylation of phenols with cinnamyl alcohols in the presence
of Re2O7-catalyst followed by Pd(II)-catalysed oxidative annulation of insitu generated o-
cinnamylphenols (Table 2). Synthesis of 2-benzyl benzo[b]furans were achieved in good yields. How-
ever, an unsymmetrical diaryl cinnamyl alcohol provides a mixture of o-cinnamylphenols (e.g., 2u and
2v, ratio: 2:1). This reflects their cationic stability under cyclization conditions which gave a mixture of
benzo[b]furans (5u and 5v) maintaining the same ratio.
Table 2. Sequential Protocol: Co-operative Catalysisa
FG
Ar/R
FG
(ii) PdCl2(CH3CN)2
BQ
(i) Re2O7
OH
CH3CN/ 80 o
t1
OH
Ar
FG
1,4-dioxane/ 80 o
t2 h
C
O
OH
C
Ar
R/Ar
3/5
1
h
Ar
Ar
entry
1
2
3
4
5
6
7
8
3/5
3a
3b
3q
3r
3s
t1 (h)
7
8
12
8
10
12
9
t2 (h)
yield (%)b
6
5
6
6
4
6
4
6
6
5
7
52
50
58
62
63
65
53
48
47
64
63
3t
5a
5b
5c
5h
5i
10
10
9
9
10
11
10
Me
Me
Ar1
Me
OH
(i)
(ii)
OH
Ar2
2u : 2v = 2:1
Ar2
5 h
O
OH
Ar1
87%
5u : 5v = 2:1
Ar1
Ar2
5u: Ar1 = pTol, Ar2 = Ph
5v: Ar1 = Ph, Ar2 = pTol
2u: Ar1 = pTol, Ar2 = Ph
2v: Ar1 = Ph, Ar2 = pTol
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aReaction conditions: (i) Alcohol (0.50 mmol), phenol (0.5 mmol), Re2O7 (5 mol %), CH3CN (2 mL)
refluxed at 80 oC. (ii) PdCl2(CH3CN)2 (5 mol %), BQ (1 equiv), 1,4-dioxane (1 mL) refluxed at 80 oC.
bIsolated yields.
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Scheme 8. Proposed mechanism for current oxidative cyclization
On the basis of the reported literature8b,c,11b,c,g and the above results, a proposed mechanism was demon-
strated in Scheme 8. The initial step involves oxa-palladation of the o-cinnamylphenol (1) to give an
intermediate I, which undergoes intramolecular 5-exo-trig cyclization to gives an intermediate II. Fol-
lowed by a β-hydride elimination of intermediate II affords an intermediate III, which undergoes sub-
sequent isomerization to form desired cyclisation product 3 or 5. Further, the Pd(0) was assumed to be
oxidized by benzoquinone (BQ) to regenerate the active Pd(II)-catalyst.
Scheme 9. Control Experimenta,b
PdCl2(CH3CN)2
Cl
BQ
Cl
1,4-dioxane
6 h, 78%
O
O
3i
9
aReaction conditions: 9 (0.05 mmol), PdCl2(CH3CN)2 (5 mol %), BQ (1 equiv), 1,4-dioxane (0.5 mL)
refluxed at 80 oC. bIsolated yields.
A control experiment was carried out to forsee wheather the reaction was really procceding through
the intermediate III as shown in Scheme 8. The compound 9 was independently synthesized and was
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further applied to the standard reaction conditions (Scheme 9).31 As expected, the desire product 3i was
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obtained in good yield.
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CONCLUSIONS
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In conclusion, we have developed an efficient synthetic route for the synthesis of highly functionalized
2-benzyl benzo[b]furans via palladium catalyzed oxidative cyclization of o-cinnmaylphenols. It is note-
worthy that this protocol provides an attractive synthetic strategy for the creation of 2-benzyl ben-
zo[b]furan derivatives in good yield and with broad substrate scope. Further, a one-pot, sequential syn-
thesis of o-cinnamylphenols, starting from readily available cinnmayl alcohols and phenols, followed by
Pd(II)-catalysed oxidative annulation has also been developed. Considering the easy availability of cin-
namyl alcohols and the water is the only by product for o-cinnamylphenols synthesis, the current strate-
gy might have superior synthetic utility compared to many methods given in Scheme 1.
EXPERIMENTAL SECTION
General Remarks: All reagents and solvents were used as supplied commercially. Commercial
PdCl2(CH3CN)2 (99.99%) were stored in a desiccator over CaCl2. Analytical thin-layer chromatography
(TLC) were performed on 0.2 mm coated Science silica gel (EM 60-F254) plates. Visualization was ac-
complished with UV light (254 nm) and exposure to either ethanolic phosphomolybdic acid (PMA),
anisaldehyde or KMnO4, CeSO4 + ammonium phosphomolybdate + 10% H2SO4, ninhydrine solution
1
followed by heating. Melting points are uncorrected. H NMR spectra were acquired on a 400 MHz
spectrometer and chemical shifts are reported relative to the residual solvent peak. 13C NMR spectra
were acquired on a 100 MHz spectrometer and chemical shifts are reported in ppm relative to the resid-
ual solvent peak. Unless noted, NMR spectra were acquired in CDCl3; individual peaks are reported as:
multiplicity, integration, coupling constant in Hz. All IR spectra were obtained as neat films and select-
ed absorbance’s are reported in cm-1.
General Procedure A: For the preparation of ortho-cinnamyl-phenols (1a-e), (1h-o), (1q-t) and
(2a-e), (2h-i), (2k-r): To a stirred solution of cinnamyl alcohol (0.5 mmol) and phenol (0.6 mmol) in
CH3CN (2.0 ml), taken in a round-bottom flask attached to a refluxed condenser, Re2O7 (5 mol %) was
o
added. Unless otherwise noted, the reaction was stirred at 80 C for the given time. The reaction was
quenched with the addition of brine solution (2 ml), followed by extraction with EtOAc (3 × 10 ml).
The combined organic layer was dried over anhydrous MgSO4. The solvent was removed under vacuum
and the crude residue was purified by flash column chromatography (EtOAc/n-Hexane) on silica gel.
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Characterization of the ortho-cinnamyl-phenols for 1a-e, 1h-o, 1q-t:
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(E)-2-(1,3-Diphenylallyl)-4-methylphenol (1a):21 The title compound was prepared using the general
procedure A; Yield: 120 mg, 80% ; Rf = 0.40 (10:90 = EtOAc/n-Hexane); Light brown liquid ; IR
(neat): 3365, 2963, 1612, 1465, 1265, 1208, 1124, 967, 825, 763 cm-1; 1H NMR (400 MHz, CDCl3): δ
7.38 (m, 3H), 7.33 – 7.29 (4H), 7.26 (m, 3H), 6.95 (d, J = 8.0 Hz, 2H), 6.72 – 6.65 (m, 2H), 6.35 (d, J =
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13
16.0 Hz, 1H), 5.08 (d, J = 8.0 Hz, 1H), 4.63 (bs, 1H), 2.25 (s, 3H); C NMR (100 MHz, CDCl3): δ
151.2, 142.1, 137.1, 131.7, 131.3, 130.2, 130.2, 129.1, 128.7, 128.6, 128.5, 128.5, 127.4, 126.8, 126.4,
116.2, 48.6, 20.7; GCLR-MS (EI, m/z): [M]+ calculated for C22H20O: 300.1; found: 300.1.
(E)-2-(1,3-Diphenylallyl)-4-methoxyphenol (1b):21 The title compound was prepared using the general
procedure A; Yield: 114 mg (72%); Rf = 0.38 (10:90 = EtOAc/n-Hexane); Light Yellow liquid; IR
(neat): 3345, 2954, 1623, 1458, 1262, 1214, 1135, 958, 841, 760 cm-1; 1H NMR (400 MHz, CDCl3): δ,
7.38 (d, J = 7.3 Hz, 2H), 7.34-7.27 (m, 6H), 7.25-7.20 (m, 2H), 6.78-6.64 (m, 4H), 6.37 (d, J = 15.9 Hz,
1H), 5.12 (d, J = 7.1 Hz, 1H), 4.90-4.20 (bs, 1H), 3.73 (s, 3H); 13C NMR (100 MHz, CDCl3): δ, 153.8,
147.4, 141.9, 137.0, 131.9, 131.0, 130.8, 128.7, 128.6, 128.5, 127.5, 126.8, 126.4, 117.0, 115.9, 112.3,
55.7, 48.6; GCLR-MS (EI, m/z): [M]+ calculated for C22H20O2: 316.1; found: 316.1.
(E)-4-(tert-Butyl)-2-(1,3-diphenylallyl)phenol (1c):21 The title compound was prepared using the gen-
eral procedure A; Yield: 139 mg, 81% ; Rf = 0.40 (10:90 = EtOAc/n-Hexane); Light brown liquid ; IR
(neat): 3365, 2963, 1612, 1465, 1265, 1208, 1124, 967, 825, 763 cm-1; 1H NMR (400 MHz, CDCl3): δ
7.41 (d, J = 8.0 Hz, 2H), 7.36 – 7.30 (6H), 7.27 – 7.26 (m, 2H), 7.21 – 7.19 (2H), 6.78 – 6.73 (m, 2H),
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6.42 (d, J = 16.0 Hz, 1H), 5.14 (d, J = 4.0Hz, 1H), 4.76 (bs, 1H), 1.30 (s, 9H); C NMR (100 MHz,
CDCl3): δ 151.2, 143.7, 142.2, 137.2, 131.9, 131.4, 128.8, 128.6, 128.60, 128.5, 127.5, 126.8, 126.8,
126.4, 124.8, 115.9, 49.2, 34.2, 31.6; GCLR-MS (EI, m/z): [M]+ calculated for C25H26O: 342.1; found:
342.1.
(E)-4-(Benzyloxy)-2-(1,3-diphenylallyl)phenol (1d): The title compound was prepared using the gen-
eral procedure A; Yield: 152 mg (77%); Rf = 0.32 (10:90 = EtOAc/n-Hexane); Brown liquid; IR (neat):
3425, 3029, 2653, 1624, 1542, 1475, 1426, 1013, 956, 845, 754 cm-1; 1H NMR (400 MHz, CDCl3): δ,
7.45-7.26 (m, 15H), 6.89-6.62 (m, 4H), 6.39 (d, J = 15.9 Hz, 1H), 5.15 (d, J = 7.1 Hz, 1H), 5.00 (s, 2H),
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4.77 (s, 1H); C NMR (100 MHz, CDCl3): δ, 153.0, 147.6, 141.9, 137.2, 137.1, 131.9, 131.1, 130.9,
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128.7, 128.7, 128.6, 127.9, 127.7, 127.5, 126.9, 126.5, 117.0, 116.9, 113.7, 70.7, 48.4; HR-MS (APCI,
m/z): [M-H]+ calculated for C28H23O2: 391.1693; found: 391.1711.
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(E)-3-(1,3-Diphenylallyl)-[1,1'-biphenyl]-4-ol (1e): The title compound was prepared using the gen-
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eral procedure A; Yield: 137 mg (76%); Rf = 0.37(10:90 = EtOAc/n-Hexane); Yellow liquid; IR (neat):
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3024, 2665, 1631, 1542, 1456, 1437, 1021, 963, 804, 751 cm-1; H NMR (400 MHz, CDCl3): δ, 7.59
(d, J = 7.2 Hz, 2H), 7.50-7.43 (m, 6H), 7.41-7.28 (9H), 6.93 (d, J = 8.2 Hz, 1H), 6.83 (dd, J = 15.9, 7.2
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Hz, 1H), 6.49 (d, J = 15.9 Hz, 1H), 5.28 (d, J = 7.1 Hz, 1H), 5.23-4.5 (bs, 1H); C NMR (100 MHz,
CDCl3): δ, 153.1, 142.1, 141.0, 137.1, 134.2, 132.1, 131.2, 129.9, 128.86, 128.84, 128.7, 128.68,
128.64, 127.6, 126.98, 126.90, 126.83, 126.82, 126.5, 116.8, 48.7; HR-MS (APCI, m/z): [M-H]+ calcu-
lated for C27H21O: 361.1587; found: 361.1615.
(E)-2-(1,3-Diphenylallyl)-4-fluorophenol (1h): The title compound was prepared using the general
procedure A; Yield: 101 mg (66%); Rf = 0.32 (10:90 = EtOAc/n-Hexane); Light Yellow liquid; IR
(neat): 3428, 2924, 1476, 1284, 1193, 1156, 1068, 984, 875, 762 cm-1; 1H NMR (400 MHz, CDCl3): δ
8.04-8.01 (m, 1H), 7.65-7.63 (m, 1H), 7.56-7.51 (1H), 7.43-7.41 (m, 1H), 7.39-7.31 (3H), 7.28-7.25
(3H), 6.88-6.84 (m, 2H), 6.78-6.75 (m, 1H), 6.64 (dd, J = 16.0, 8.0 Hz, 1H), 6.36 (d, J = 16.0 Hz, 1H),
5.12 (d, J = 8.0 Hz, 1H), 4.98 (bs, 1H); 13C NMR (100 MHz, CDCl3): δ 157.31 (d, J = 238.3 Hz, 1C),
149.5 (d, J = 2.2 Hz, 1C), 145.2, 141.5, 132.3, 131.3 (d, J = 6.7 Hz, 1C), 130.5, 128.8 (2C), 128.62
(2C), 128.61 (2C), 127.6, 127.0, 126.4 (2C), 122.1, 117.2 (d, J = 8.1 Hz, 1C), 116.20 (d, J = 23.8 Hz,
1C), 114.2 (d, J = 23.1 Hz), 48.2; HR-MS (APCI, m/z): [M-H]+ calculated for C21H16FO: 303.1180;
found: 303.1187.
(E)-4-Chloro-2-(1,3-diphenylallyl)phenol (1i): The title compound was prepared using the general
procedure A; Yield: 107 mg (67%); Rf = 0.37 (10:90 = EtOAc/n-Hexane); Brown Liquid; IR (neat):
3463, 2921, 1508, 1476, 1317, 1189, 1048, 987, 765 cm-1; 1H NMR (400 MHz, CDCl3): δ 7.65 – 7.60
(1H), 7.53 – 7.43 (1H), 7.36 (m, 4H), 7.28 (m, 4H), 7.13 – 7.10 (2H), 6.75 (d, J = 8.0 Hz, 1H), 6.64 (dd,
J = 16.0, 8.0 Hz, 1H), 6.37 (d, J = 16.0 Hz, 1H), 5.11 (s, 1H), 5.09 (bs, 1H); 13C NMR (100 MHz,
CDCl3): δ 152.1, 141.3, 136.8, 132.3, 131.4, 130.4, 129.5, 129.0, 128.8, 128.6, 128.6, 127.8, 127.7,
127.1, 126.5, 125.8, 48.3; HR-MS (APCI, m/z): [M-H]+ calculated for C21H16ClO: 319.0884; found:
319.0911.
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(E)-4-Bromo-2-(1,3-diphenylallyl)phenol (1j): The title compound was prepared using the general
procedure A; Yield: 107 mg (63%); Rf = 0.35 (10:90 = EtOAc/n-Hexane); Brown Liquid; IR (neat):
3386, 3022, 1535, 1442, 1252, 1135, 1051, 924, 821, 752, cm-1; 1H NMR (400 MHz, CDCl3): δ 7.65 –
7.60 (1H), 7.53 – 7.43 (1H), 7.36 (m, 4H), 7.28 (m, 4H), 7.13 – 7.10 (2H), 6.75 (d, J = 8.0 Hz, 1H), 6.64
(dd, J = 16.0, 8.0 Hz, 1H), 6.37 (d, J = 16.0 Hz, 1H), 5.11 (s, 1H), 5.09 (bs, 1H); 13C NMR (100 MHz,
CDCl3): δ 152.1, 141.3, 136.8, 132.3, 131.4, 130.4, 129.5, 129.0, 128.8, 128.6, 128.5, 127.8, 127.7,
127.1, 126.5, 125.8, 48.3; HR-MS (APCI, m/z): [M-H]+ calculated for C21H16BrO: 363.0379; found:
363.0385.
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(E)-2-(1,3-Diphenylallyl)-4-iodophenol (1k): The title compound was prepared using the general pro-
cedure A; Yield: 134 mg (66%); Rf = 0.36 (10:90 = EtOAc/n-Hexane); Brown Liquid; IR (neat): 3341,
1475, 1410, 1084, 1018, 947, 814, 738 cm-1; 1H NMR (400 MHz, CDCl3): δ 7.52 (m, 1H), 7.42 – 7.38
(5H), 7.31 (m, 2H), 7.26 (m, 2H), 7.13 (s, 1H), 7.10 (d, J = 8.0 Hz, 1H), 6.75 (d, J = 8.0 Hz, 1H), 6.64
(dd, J = 16.0, 8.0 Hz, 1H), 6.37 (d, J = 16.0 Hz, 1H), 5.11 (s, 1H), 5.09 (bs, 1H); 13C NMR (100 MHz,
CDCl3): δ 152.1, 145.4, 141.4, 136.7, 132.4, 131.3, 130.4, 128.7, 128.6, 128.5, 127.7, 127.6, 126.5,
125.7, 122.0, 117.5, 48.2; HR-MS (APCI, m/z): [M-H]+ calculated for C21H16IO: 411.0240; found:
411.0238.
(E)-2,4-Dichloro-6-(1,3-diphenylallyl)phenol (1l): The title compound was prepared using the general
procedure A; Yield: 42 mg (58%); Rf = 0.33 (10:90 = EtOAc/n-Hexane); Light brown Liquid; IR (neat):
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3427, 3375, 3031, 2905, 1521, 1042, 957, 719cm-1; H NMR (400 MHz, CDCl3): δ 7.60 – 7.58 (m,
2H), 7.50 – 7.46 (2H), 7.45 – 7.41(3H), 7.38 – 7.30 (4H), 6.93 (d, J = 8.0 Hz, 1H), 6.83 (dd, J = 16.0,
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8.0 Hz, 1H), 6.49 (d, J = 16.0 Hz, 1H), 5.28 (d, J = 8.0 Hz, 1H), 5.11 (bs, 1H); C NMR (100 MHz,
CDCl3): δ 153.1, 142.1, 141.0, 137.1, 134.2, 132.1, 131.2, 129.9, 128.9, 128.8, 128.6, 127.6, 126.9,
126.8, 126.5, 116.8, 48.7; HR-MS (APCI, m/z): [M-H]+ calculated for C21H15Cl2O: 353.0494; found:
353.0485.
(E)-2-Bromo-4-chloro-6-(1,3-diphenylallyl)phenol (1m): The title compound was prepared using the
general procedure A; Yield: 107 mg (55%); Rf = 0.34 (10:90 = EtOAc/n-Hexane); Yellow Liquid; IR
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(neat):3422, 2931, 2845, 15847, 1486, 1452, 1346, 1261, 1107, 968, 819, 745cm-1; H NMR (400
MHz, CDCl3): δ 8.03 (d, J = 8.0 Hz, 1H), 7.58 – 7.83 (2H), 7.41 – 7.33 (4H), 7.31 – 7.26 (3H), 6.86 –
6.74 (m, 2H), 6.63 (dd, J = 16.0, 8.0 Hz, 1H), 6.36 (d, J = 16.0 Hz, 1H), 5.12 (d, J = 8.0 Hz, 1H), 4.98
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(bs, 1H); 13C NMR (100 MHz, CDCl3): δ 154.9, 149.1, 137.1, 131.1, 131.0, 129.0, 128.7, 128.6, 128.6,
127.5, 126.7, 126.5, 117.1, 115.9, 112.4, 55.7, 48.6; HR-MS (APCI, m/z): [M-H]+ calculated for
C21H15BrClO: 398.9989; found: 398.9980.
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(E)-4-Chloro-2-(1,3-diphenylallyl)-6-methylphenol (1n): The title compound was prepared using the
general procedure A; Yield: 102 mg (60%); Rf = 0.29 (10:90 = EtOAc/n-Hexane); Yellow Liquid; IR
(neat): 3421, 2934, 1467, 1258, 1196, 1142, 1019, 970, 843, 736 cm-1; 1H NMR (400 MHz, CDCl3): δ
7.44 – 7.35 (4H), 7.29 – 7.21 (5H), 6.95 (m, 2H), 6.72 (s, 1H), 6.68 (m, 1H), 6.35 (d, J = 16.0 Hz, 1H),
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5.08 (d, J = 8.0 Hz, 1H), 4.63 (bs, 1H), 2.25 (s, 3H); C NMR (100 MHz, CDCl3): δ 151.3, 142.2,
137.2, 131.7, 131.4, 130.2, 130.2, 129.1, 128.7, 128.6, 128.5, 128.4, 127.4, 126.7, 126.4, 116.2, 48.5,
20.7; HR-MS (APCI, m/z): [M-H]+ calculated for C22H18ClO: 333.1040; found: 333.1035.
(E)-2-Benzyl-4-chloro-6-(1,3-diphenylallyl)phenol (1o): The title compound was prepared using the
general procedure A; Yield: 130 mg (62%); Rf = 0.32 (10:90 = EtOAc/n-Hexane); Yellow Liquid; IR
(neat): 3326, 2937, 1483,1257, 1194, 1148, 1052, 953, 754cm-1; 1H NMR (400 MHz, CDCl3): δ 7.3 (m,
3H), 7.33 –7.28(6H), 7.26 – 7.25(4H), 7.20 (m, 2H), 7.02 (dd, J = 8.0, 4.0 Hz, 2H), 6.62 (dd, J = 16.0,
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8.0 Hz, 1H), 6.34 (d, J = 16.0 Hz, 1H), 5.03 (d, J = 8.0 Hz, 1H), 4.80 (s, 1H), 3.94 (s, 2H); C NMR
(100 MHz, CDCl3): δ 150.4, 141.0, 139.0, 136.7, 132.5, 131.4, 130.2, 129.8, 129.1, 128.9, 128.8,
128.7, 128.6, 128.6, 127.7, 127.6, 127.3, 126.6, 126.5, 125.6, 48.7, 36.4; HR-MS (APCI, m/z): [M-H]+
calculated for C28H22ClO: 409.1354; found: 409.1355.
(E)-4-Bromo-2-(1,3-diphenylallyl)-6-methoxyphenol (1q): The title compound was prepared using
the general procedure A; Yield: 132 mg (67%); Rf = 0.26 (10:90 = EtOAc/n-Hexane); Yellow Liquid;
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IR (neat): 3362, 3024, 2956, 1478, 1465, 1236, 1145, 1014, 925, 845, 763 cm-1; H NMR (400 MHz,
CDCl3): δ 7.37 – 7.30 (3H), 7.30 – 7.26 (4H), 7.23 (m, 2H), 6.75 (m, 2H), 6.69 – 6.65(2H), 6.37 (d, J =
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16.0 Hz, 1H), 5.12 (d, J = 4.0 Hz, 1H), 4.57 (bs, 1H), 3.73 (s, 3H); C NMR (100 MHz, CDCl3): δ
153.8, 147.5, 141.9, 137.0, 131.9, 131.1, 130.7, 128.7, 128.6, 128.5, 127.3, 126.8, 126.3, 117.0, 115.9,
112.3, 55.7, 48.6; HR-MS (APCI, m/z): [M-H]+ calculated for C22H18BrO2: 393.0484; found:
393.0476.
(E)-2-(1,3-Diphenylallyl)-3,5-dimethylphenol (1r): The title compound was prepared using the gen-
eral procedure A; Yield: 124 mg (78%); Rf = 0.32 (40:60 = Dichloromethane/n-Hexane); Yellow
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Liquid; IR (neat): 3358, 3021, 2966, 1468, 1314, 1240, 1142, 1012, 933, 856, 756cm-1; H NMR (400
MHz, CDCl3): δ 7.43 – 7.42 (2H), 7.36 – 7.33 (5H), 7.31 – 7.25 (3H), 6.87 (dd, J = 16.0, 4.0 Hz, 1H),
6.69 (s, 1H), 6.56 (s, 1H), 6.50 (d, J = 16.0 Hz, 1H), 5.29 (d, J = 8.0 Hz, 1H), 5.00 (s, 1H), 2.37 (s, 3H),
2.30 (s, 3H).13C NMR (100 MHz, CDCl3): δ 154.5, 141.8, 137.9, 137.6, 137.1, 132.5, 129.9, 128.8,
128.6, 127.8, 127.6, 126.8, 126.5, 124.3, 124.1, 115.9, 46.5, 20.9, 20.7; HR-MS (APCI, m/z): [M-H]+
calculated for C23H22O: 313.1593; found: 313.1571.
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(E)-6-(1,3-Diphenylallyl)-2,3-dimethylphenol (1s): The title compound was prepared using the gen-
eral procedure A; Yield: 121 mg (77%); Rf = 0.33 (40:60 = Dichloromethane/n-Hexane); Light Yellow
Liquid; IR (neat): 3362, 3024, 2956, 1478, 1465, 1236, 1145, 1014, 925, 845, 763 cm-1; 1H NMR (400
MHz, CDCl3): δ 7.45 – 7.43 (3H), 7.40 – 7.32 (5H), 7.30 – 7.26 (2H), 6.96 (d, J = 8.0 Hz, 1H), 6.83 (d,
J = 8.0 Hz, 1H), 6.77 (dd, J = 16.0, 8.0 Hz, 1H), 6.45 (d, J = 16.0 Hz, 1H), 5.12 (d, J = 8.0 Hz, 1H), 4.90
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(s, 1H), 2.34 (s, 3H), 2.22 (s, 3H); C NMR (100 MHz, CDCl3): δ 151.7, 142.1, 137.1, 136.7, 131.9,
131.4, 128.9, 128.7, 128.6, 127.6, 127.0, 126.6, 126.5, 126.5, 123.5, 122.2, 49.2, 20.2, 11.9; HR-MS
(APCI, m/z): [M-H]+ calculated for C23H21O: 313.1587; found: 313.1567.
(E)-2-(1,3-Diphenylallyl)-3,5,6-trimethylphenol (1t): The title compound was prepared using the gen-
eral procedure A; Yield: 132 mg (80%); Rf = 0.35 (40:60 = Dichloromethane/n-Hexane); Light Yellow
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Liquid; IR (neat): 3348, 3014, 2956, 1453, 1435, 1232, 1134, 1012, 933, 856, 758cm-1; H NMR (400
MHz, CDCl3): δ 7.44 – 7.42 (3H), 7.37 – 7.35 (4H), 7.33 – 7.25 (3H), 6.86 (dd, J = 16.0, 8.0 Hz, 1H),
6.70 (s, 1H), 6.50 (d, J = 16.0 Hz, 1H), 5.29 (d, J = 8.0 Hz, 1H), 5.08 (s, 1H), 2.36 (s, 3H), 2.27 (s, 3H),
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2.13 (s, 3H); C NMR (100 MHz, CDCl3): δ 152.6, 141.6, 137.0, 136.4, 134.1, 132.7, 129.8, 128.9,
128.6, 127.9, 127.6, 126.9, 126.5, 124.5, 124.1, 122.1, 46.9, 20.5, 19.9, 11.7; HR-MS (APCI, m/z):
[M-H]+ calculated for C24H24O: 327.1749; found: 327.1756.
Compound 1f-h, 1p and 1u-v were not separable in column chromatography (it was having the same Rf
value with their corresponding phenol counterpart).
Characterization of the ortho-cinnamyl phenol 2a-e, 2h-o and 2s-t: The title compound was prepared
using the general procedure A:
(E)-2-(1,3-Di-p-tolylallyl)-4-methylphenol (2a): The title compound was prepared using the general
procedure A: Yield: 126 mg (77%); Rf = 0.31 (10:90 = EtOAc/n-Hexane); Yellow Liquid; IR (neat):
3433,2936, 1578, 1523, 1235, 1199, 1035, 956, 801, 765cm-1; 1H NMR (400 MHz, CDCl3): δ 7.32 (d,
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J = 8.0 Hz, 2H), 7.20 – 7.18 (3H), 7.15 – 7.10 (3H), 6.99 (m,2H), 6.74 (d, J = 8.0 Hz, 1H), 6.67 (dd, J =
12.0, 4.0 Hz, 1H), 6.37 (d, J = 16.0 Hz, 1H), 5.06 (d, J = 8.0 Hz, 1H), 4.80 (bs, 1H), 2.37 (s, 3H), 2.36
(s, 3H), 2.29 (s, 3H); 13C NMR (100 MHz, CDCl3):δ 151.3, 139.1, 137.2, 136.4, 134.4, 131.5, 130.5,
130.2, 130.1, 129.5, 129.4, 129.3, 128.5, 128.4, 126.4, 116.3, 48.4, 21.2, 21.1, 20.7; HR-MS (APCI,
m/z): [M-H]+ calculated for C24H23O: 327.1743; found: 327.1738.
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(E)-2-(1,3-Bis(4-fluorophenyl)allyl)-4-methylphenol (2b): The title compound was prepared using the
general procedure A; Yield: 110 mg (65%); Rf = 0.30 (10:90 = EtOAc/n-Hexane); Yellow Liquid; IR
(neat): 3421, 2944, 1489, 1457, 1281, 1047, 935, 754cm-1;1H NMR (400 MHz, CDCl3): δ 7.35 – 7.31
(2H), 7.23 – 7.19 (2H), 7.02 – 6.91 (6H), 6.69 (d, J = 8.0 Hz, 1H), 6.57 (dd, J = 16.0, 8.0 Hz, 1H), 6.28
(d, J = 16.0 Hz, 1H), 5.08 (d, J = 8.0 Hz, 1H), 4.65 (s, 1H), 2.26 (s, 3H); 13C NMR (100 MHz, CDCl3):
δ 150.9, (d, J = 238.3 Hz, 1C), 137.9, 137.9,(d, J = 3.3 Hz, 1C) 133.2, 133.1 (2C), 131.0, 130.6, 130.3,
130.1 (2C), 129.0, 128.5, 127.9, 127.8, (d, J = 8.0 Hz, 1C), 116.1 (2C),115.5 (d, J = 4.5 Hz, 1C),
115.3,(d, J = 4.2 Hz, 1C), 47.5, 20.7; HR-MS (APCI, m/z): [M-H]+ calculated for C22H17F2O:
335.1242; found: 335.1237.
(E)-2-(1,3-Bis(4-Chlorophenyl)allyl)-4-methylphenol (2c): The title compound was prepared using
the general procedure A: Yield: 116 mg (63%); Rf = 0.33 (10:90 = EtOAc/n-Hexane); Light Yellow
Liquid; IR (neat): 3254, 3104, 1478, 1424, 1275, 1204, 1112, 1042, 957, 754cm-1; 1H NMR (400 MHz,
CDCl3): δ 7.31 – 7.25 (6H), 7.19 (d, J = 8.0 Hz, 2H), 6.97 – 6.93(2H), 6.69 (d, J = 8.0 Hz, 1H), 6.64
(dd, J = 16.0, 8.0 Hz, 1H), 6.28 (dd, J = 16.0, 4.0 Hz, 1H), 5.11 (d, J = 8.0 Hz, 1H), 4.74 (s, 1H), 2.27
(s, 3H); 13C NMR (100 MHz, CDCl3): δ 150.9, 140.8, 135.5, 133.1, 132.4, 131.8, 130.7, 130.4, 130.1,
129.9, 128.8, 128.7, 128.6, 128.5, 127.6, 116.1, 47.5, 20.7; HR-MS (APCI, m/z):[M-H]+ calculated for
C22H17Cl2O: 367.0651; found: 367.0653.
(E)-2-(1,3-Bis(4-Bromophenyl)allyl)-4-methylphenol (2d):22 The title compound was prepared using
the general procedure A; Yield: 136 mg (61%); Rf = 0.35 (10:90 = EtOAc/n-Hexane); Light Yellow
Liquid; IR (neat): 3356, 3026, 1494, 1487, 1325, 1245, 1104, 1008, 956, 824, 752 cm-1; 1H NMR (400
MHz, CDCl3): δ 7.44– 7.41 (4H), 7.23 (d, J = 8.0 Hz, 2H), 7.12 (d, J = 8.0 Hz, 2H), 6.96 – 6.91 (2H),
6.68 (d, J = 8.0 Hz, 1H), 6.63(t, J = 8.0 Hz, 1H), 6.26 (d, J = 16.0 Hz, 1H), 5.08 (d, J = 8.0 Hz, 1H),
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4.65 (bs, 1H), 2.26 (s, 3H); C NMR (100 MHz, CDCl3): δ 150.9, 141.3, 135.9, 131.9, 131.6, 131.6,
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130.8, 130.4, 130.4, 130.1, 128.7, 128.6, 127.9, 121.3, 120.6, 116.1, 47.6, 20.7; GCLR-MS (EI,
m/z):[M]+ calculated for C22H18Br2O: 455.9; found: 455.9.
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(E)-2-(1,3-Di([1,1'-Biphenyl]-4-yl)allyl)-4-methylphenol (2e): The title compound was prepared using
the general procedure A; Yield: 172 mg (78%); Rf = 0.36 (10:90 = EtOAc/n-Hexane); Light Yellow
Liquid; IR (neat): 3324, 3048, 1463, 1410, 1281, 1232, 1108, 1072, 947, 764 cm-1; 1H NMR (400 MHz,
CDCl3): δ 7.64 – 7.58 (8H), 7.52 – 7.49 (4H), 7.47– 7.45 (m, 2H), 7.39 – 7.35 (m, 4H), 7.05 (m, 1H),
7.02 (dd, J = 8.0, 4.0 Hz, 1H), 6.82 (d, J = 16.0, 8.0 Hz, 1H), 6.77 (d, J = 8.0, 1H), 6.49 (d, J = 16.0 Hz,
1H), 5.22 (d, J = 8.0 Hz, 1H), 4.85 (s, 1H), 2.33 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 151.2, 141.4,
140.9, 140.8, 140.3, 139.6, 136.2, 131.6, 131.4, 130.3, 130.3, 130.1, 129.2, 129.1, 128.8, 128.8, 128.6,
127.4, 127.3, 127.3, 127.1, 127.0, 126.9, 116.3, 48.3, 20.8; HR-MS (APCI, m/z): [M-H]+ calculated for
C34H27O: 451.2056; found: 451.2064.
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2-Cinnamyl-4-methylphenol (2h):23 The title compound was prepared using the general procedure A;
Yield: 85 mg (76%); Rf = 0.36 (10:90 = EtOAc/n-Hexane); Light yellow liquid; IR (neat): 3368, 2967,
1
1603, 1485, 1271, 1235, 1206, 1147, 966, 834, 766cm-1; H NMR (400 MHz, CDCl3): δ, 7.38 (d, J =
7.3 Hz, 2H), 7.32 (t, J = 7.5 Hz, 2H), 7.24 (t, J = 7.2 Hz, 1H), 7.00 (s, 1H), 6.96 (d, J = 8.1 Hz, 1H),
6.73 (d, J = 8.1 Hz, 1H), 6.53 (d, J = 15.9 Hz, 1H), 6.41 (m, 1H), 4.92 (s, 1H), 3.56 (d, J = 6.3 Hz, 2H),
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2.30 (s, 3H); C NMR (100 MHz, CDCl3): δ, 151.7, 137.2, 131.4, 131.0, 130.2, 128.5, 128.3, 128.1,
127.3, 126.2, 125.5, 115.6, 34.1, 20.5; GCLR-MS (ESI, m/z): [M]+ calculated for C16H16O: 224.1;
found: 224.1.
2-Cinnamyl-4-methoxyphenol (2i):24 The title compound was prepared using the general procedure A;
Yield: 89 mg (74%); Rf = 0.34 (10:90 = EtOAc/n-Hexane); Light brown liquid ; IR (neat): 3358, 2947,
1
1613, 1465, 1251, 1235, 1210, 1137, 948, 832, 760cm-1; H NMR (400 MHz, CDCl3): δ 7.35 – 7.33
(2H), 7.30 – 7.26 (2H), 7.21 – 7.18 (m, 1H), 6.76 – 6.73 (2H), 6.68 (dd, J = 8.0, 4.0 Hz, 1H), 6.49 (d, J
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= 16.0 Hz, 1H), 6.39 – 6.32 (1H), 4.58 (s, 1H), 3.75 (s, 3H), 3.52 (d, J = 4.0 Hz, 2H); C NMR (100
MHz, CDCl3): δ, 151.7, 137.2, 131.4, 131.0, 130.2, 128.5, 128.3, 128.1, 127.3, 126.2, 125.5, 115.6,
34.1, 20.5; GCLR-MS (EI, m/z): [M]+ calculated for C16H16O2: 240.1; found: 240.1.
(E)-4-Methyl-2-(4-phenylbut-3-en-2-yl)phenol (2j):25 The title compound was prepared using the gen-
eral procedure A; Yield: 72 mg (60%); Rf = 0.34 (10:90 = EtOAc/n-Hexane); Light brown liquid; IR
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(neat): 2954, 1684, 1475, 1249, 1263, 1208, 1147, 1023, 949, 850, 760 cm-1; H NMR (400 MHz,
CDCl3): δ 7.38 – 7.36 (2H), 7.31 – 7.27 (2H), 7.23(m, 1H), 7.0 – 6.91 (2H), 6.70 (d, J = 8.0 Hz, 1H),
6.53 – 6.40 (2H), 4.83 (s, 1H), 3.86 (q, J = 16.0, 8.0 Hz, 1H), 2.28 (s, 3H), 1.48 (d, J = 8.0 Hz, 3H); 13C
NMR (100 MHz, CDCl3): δ 151.2, 137.2, 134.1, 130.5, 130.2, 129.2, 128.6, 128.5, 127.9, 127.3, 126.3,
115.9, 36.8, 20.7, 19.5; GCLR-MS (EI, m/z):[M]+ calculated for C17H18O: 238.1; found: 238.1.
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(E)-4-Methoxy-2-(4-phenylbut-3-en-2-yl)phenol (2k):25 The title compound was prepared using the
general procedure A; Yield: 93 mg (73 %); Rf = 0.34 (10:90 = EtOAc/n-Hexane); Light brown liquid;
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IR (neat): 2956, 1680, 1465, 1253, 1260, 1218, 1152, 1026, 952, 847, 753cm-1; H NMR (400 MHz,
CDCl3) δ 7.37-7.35 (2H), 7.31-7.27 (2H), 7.22-7.29 (m, 1H), 6.79 (d, J = 4.0 Hz, 1H), 6.74 (d, J = 4.0
Hz, 1H), 6.67 (dd, J =12.0, 8.0 Hz, 1H), 6.50 (d, J = 16.0 Hz, 1H), 6.41 (dd, J = 16.0, 8.0 Hz, 1H), 4.87
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(s, 1H), 3.88 (m, 1H), 3.77 (s, 3H), 1.47 (d, J = 8.0 Hz, 3H); C NMR (100 MHz, CDCl3): δ 153.9,
147.5, 137.2, 133.8, 132.2, 129.42, 128.5, 127.3, 126.3, 116.7, 114.0, 111.9, 55.8, 55.7, 36.8, 36.8, 19.5;
HR-MS (APCI, m/z): [M]+ calculated for C17H18O2: 254.1307; found: 254.1293.
(E)-4-Methyl-2-(4-(1-methyl-1H-indol-3-yl)but-3-en-2-yl)phenol (2l): The title compound was pre-
pared using the general procedure A; Yield: 82 mg (56%); Rf = 0.35 (40:60 = Dicholoromethane/n-
Hexane); Yellow liquid ; IR (neat): 2964, 2132, 1845, 1712, 1613, 1472, 1329, 1243, 1234, 1145, 967,
863, 756 cm-1; 1H NMR (400 MHz, CDCl3): δ 8.33 – 8.31 (m, 1H), 7.58 (s, 1H), 7.36 – 7.27 (3H), 7.22
– 7.18 (1H), 7.02 (d, J = 4.0 Hz, 1H), 6.92 (dd, J = 8.0, 2.0 Hz, 1H), 6.80 (d, J = 8.0 Hz, 1H), 6.49 (d, J
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= 3.4 Hz, 1H), 4.01 – 3.98 (1H), 3.78 (s, 3H), 2.29 (s, 3H), 1.49 (d, J = 4.0 Hz, 3H); C NMR (100
MHz, CDCl3): δ 151.6, 139.7, 137.9, 137.5, 134.6, 131.2, 129.7, 128.5, 126.2, 125.3, 124.1, 123.0,
122.0, 117.9, 115.8, 109.9, 36.3, 33.6, 20.7, 19.8; HR-MS (APCI, m/z): [M+H]+ calculated for
C20H22NO: 292.1701; found: 292.1723.
(E)-4-Methyl-2-(4-(1-methyl-1H-pyrrol-2-yl)but-3-en-2-yl)phenol (2m): The title compound was
prepared using the general procedure A; Yield: 63 mg (52%); Rf = 0.32 (40:60 = Dicholoromethane/n-
Hexane); Yellow liquid; IR (neat): 2964, 2132, 1845, 1712, 1613, 1472, 1329, 1243, 1234, 1145, 967,
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863, 756 cm-1; H NMR (400 MHz, CDCl3): δ 7.88 (d, J = 8.0 Hz, 1H), 7.41– 7.40 (m, 1H), 7.34 –
7.31 (1H), 7.25 (m, 1H), 7.03 (s, 1H), 6.94 (dd, J = 8.0, 4.0 Hz, 1H), 6.78 (d, J = 8.0 Hz, 1H), 6.51 (m,
1H), 4.01 – 3.96 (1H), 3.91 (s, 3H), 2.31 (s, 3H), 1.52 (d, J = 4.0 Hz, 3H); 13C NMR (100 MHz,
CDCl3): δ 164.7, 151.4, 137.4, 134.4, 132.1, 131.0, 129.9, 128.5, 127.8, 127.1, 126.2, 115.8, 114.4,
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55.6, 36.3, 20.7, 19.7; HR-MS (APCI, m/z): [M+H]+ calculated for C16H20NO: 242.1545; found:
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(E)-2-(4-(Furan-2-yl)but-3-en-2-yl)-4-methylphenol (2n):25 The title compound was prepared using
the general procedure A; Yield: 60 mg (53%); Rf = 0.35 (40:60 = Dichloromethane/n-Hexane); Light
brown liquid; IR (neat): 2834, 1724, 1652, 1421, 1253, 1241, 1150, 1027, 956, 875, 756 cm-1; 1H NMR
(400 MHz, CDCl3) δ 7.38 – 7.36 (d, J = 8.0 Hz, 1H), 7.28 (m, 1H), 7.22 (d, J = 8.0 Hz, 1H), 7.00 (s,
1H), 6.93 (dd, J = 8.0, 4.0 Hz, 1H), 6.70 (d, J = 8.0 Hz, 1H), 6.51 (d, J = 16.0 Hz, 1H), 6.43 (dd, J =
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16.0, 8.0 Hz, 1H), 4.83 (bs, 1H), 3.86 (m, 1H), 2.28 (s, 3H), 1.48 (d, J = 8.0 Hz, 3H); C NMR (100
MHz, CDCl3): δ 151.3, 151.2, 137.2, 134.1, 130.5, 130.2, 129.2, 128.5, 127.9, 127.3, 126.2, 115.9,
36.8, 20.7, 19.5; HR-MS (APCI, m/z): [M-H]+ calculated for C15H15O2: 227.1072; found: 227.1069.
(E)-2-(1-Cyclohexyl-3-phenylallyl)-4-methylphenol (2o): The title compound was prepared using the
general procedure A; Yield: 72 mg (62%); Rf = 0.35 (10:90 = EtOAc/n-Hexane); Light brown liquid; IR
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(neat): 2956, 1663, 1524, 1455, 1245, 1239, 1205, 1124, 957, 862, 752cm-1; H NMR (400 MHz,
CDCl3): δ 7.35 – 7.33 (2H), 7.29 – 7.26 (2H), 7.21 – 7.25 (m, 1H), 6.96 (d, J = 2.0 Hz, 1H), 6.85 (dd, J
= 8.0, 4.0 Hz, 1H), 6.63 (d, J = 8.0 Hz, 1H), 6.43 – 6.41 (m, 2H), 4.58 (s, 1H), 3.39 (m, 1H), 2.27 (s,
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3H), 1.96 (d, J = 12.0 Hz, 1H), 1.80 – 1.72 (2H), 1.62 (2H), 1.26 – 1.12 (4H), 1.02 – 0.82 (2H); C
NMR (100 MHz, CDCl3): δ 150.9, 137.6, 132.3, 130.4, 130.1, 129.6, 129.5, 128.4, 127.4, 126.9, 126.1,
115.7, 50.0, 41.2, 31.8, 31.4, 26.6, 26.4, 26.4, 20.7; HR-MS (APCI, m/z):[M+H]+ calculated for
C22H26O: 307.2068; found: 307.2057.
Compound 2f-g and 2p-r was not separable in column chromatography (it was having the same Rf val-
ue with their corresponding phenol counterpart).
Preparation of 2s & 2t: 2s and 2t were synthesized by a previously reported method and the characteri-
zation data for these compound were matched with the previously reported data.30
2-Allyl-4-methoxyphenol (2s): Rf = 0.35 (10:90 = EtOAc/n-Hexane); Light Yellow Liquid; IR (neat):
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3326, 2989, 2931, 1446, 1405, 1182, 1034, 965, 846, 739 cm-1; H NMR (400 MHz, CDCl3): δ, 6.77
(d, J = 8.0 Hz, 1H), 6.72 – 6.69 (2H), 6.08 – 6.0 (1H), 5.20 – 5.16 (2H), 4.88 – 4.84 (m, 1H), 3.79 (s,
3H), 3.41 (d, J = 8.0 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ, 153.7, 148.0, 136.2, 126.6, 116.5,
116.5, 115.9, 112.6, 55.7, 35.3; GCLR-MS (EI, m/z): [M]+ calculated for C10H12O2: 164.0; found:
164.0.
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2-Allyl-4-methylphenol (2t): Rf = 0.35 (05:95 = EtOAc/n-Hexane); Light Yellow Liquid; IR (neat):
3348, 3014, 2956, 1453, 1435, 1232, 1134, 1012, 933, 856, 758 cm-1; 1H NMR (400 MHz, CDCl3): δ,
6.94 – 9.92 (2H), 6.71 (d, J = 8.0 Hz, 1H), 6.07 – 5.97 (1H), 5.17 (dd, J = 8.0, 4.0 Hz, 1H), 5.14 (t, J =
4.0 Hz, 1H), 4.86 (s, 1H), 3.38 (d, J = 8.0 Hz, 2H), 2.27 (s, 3H); 13C NMR (100 MHz, CDCl3): δ,
151.8, 136.6, 130.9, 130.1, 128.3, 125.1, 116.4, 115.7, 35.1, 20.5; GCLR-MS (EI, m/z): [M]+ calculat-
ed for C10H12O: 148.08; found: 148.1.
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General Procedure B: Synthesis of 2-benzyl benzo[b]furan via palladium catalyzed oxidative
cyclization of o-cinnamylphenols: o-Cinnamylphenols 1 or 2 (0.20 mmol) in 1,4-dioxane (1 mL) was
taken in a 5 mL round bottom flask, PdCl2(CH3CN)2 (5 mol %) and benzoquinone (1 equiv) was added.
The reaction mixture containing RB flask was fitted with a reflux condenser, placed into a preheated oil
bath at 80 ºC. After consumption of starting material (followed by TLC analysis), the mixture was
cooled to room temperature and filtered through celite. The filtrate was diluted with H2O (10 mL) fol-
lowed by washing with ethylacetate (3 x 10 mL). The organic extract was dried over anhydrous MgSO4.
The solvents were removed under reduced pressure to provide the crude product 3 or 5, respectively,
which was purified by flash chromatography on silica-gel using n-hexane/ethylacetate as eluent.
Characterization of benzo[b]furan products (3a-v)
&
(5a-v): 2-Benzyl-5-methyl-3-
phenylbenzofuran (3a):26a The title compound was prepared using the general procedure B; Yield: 50
o
mg (85%); Rf = 0.41 (02:98 = EtOAc/n-Hexane); mp:148-150 C; IR (neat): 3065, 2920, 1614, 1462,
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1448, 1321, 1263, 1223, 1056, 1018, 965, 820, 765 cm-1; H NMR (400 MHz, CDCl3): δ, 7.56 – 7.49
(4H), 7.41 (m, 2H), 7.36 – 7.25 (6H), 7.12 (d, J = 8.0Hz, 1H), 4.23 (s, 2H), 2.46 (s, 3H); 13C NMR (100
MHz, CDCl3): δ, 152.8, 152.7, 138.1, 132.7, 132.2, 129.1, 128.9, 128.8, 128.7, 128.5, 127.3, 126.6,
125.2, 119.6, 118.2, 110.7, 32.9, 21.4; GCLR-MS (EI, m/z): [M]+ calculated for C22H18O: 298.1;
found: 298.1.
2-Benzyl-5-methoxy-3-phenylbenzofuran (3b):26a The title compound was prepared using the general
o
procedure B; Yield: 58 mg (92%); Rf = 0.36 (05:95 = EtOAc/n-Hexane); White solid; mp:165-168 C;
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IR (neat): 3057, 2926, 1548, 1484, 1460, 1444, 1278, 1131, 1065, 1051, 912, 885, 823, 748, cm-1; H
NMR (400 MHz, CDCl3): δ 7.51-7.47 (m, 4H), 7.41-7.34 (m, 2H), 7.30 (d, J = 7.2 Hz, 2H), 7.27-7.22
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(m, 3H), 7.06 (d, J = 2.5 Hz, 1H), 6.89 (dd, J = 8.9, 2.6 Hz, 1H), 4.20 (s, 2H), 3.82 (s, 3H); C NMR
(100 MHz, CDCl3): δ 156.1, 153.5, 149.3, 137.9, 132.6, 129.2, 129.0, 128.9, 128.6, 128.5, 127.3,
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126.6, 118.5, 112.5, 111.6, 102.4, 56.0, 33.0; GCLR-MS (EI, m/z): [M]+ calculated for C22H18O2:
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2-Benzyl-5-(tert-butyl)-3-phenylbenzofuran (3c):26a The title compound was prepared using the gen-
eral procedure B; Yield: 61 mg (90%); Rf = 0.38 (05:95 = EtOAc/n-Hexane); White solid ; mp:175-176
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oC; IR (neat): 3086, 2932, 1628, 1468, 1436, 1327, 1243, 1125, 1056, 1016, 958, 829, 760 cm-1; H
NMR (400 MHz, CDCl3): δ, 7.56 (d, J = 1.5 Hz, 1H), 7.52-7.48 (m, 4H), 7.40-7.33 (m, 3H), 7.25 (5H),
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4.18 (s, 2H), 1.35 (s, 9H); C NMR (100 MHz, CDCl3): δ, 152.7, 152.5, 145.9, 138.0, 132.7, 129.1,
128.8, 128.5, 128.4, 128.2, 127.2, 126.5, 121.8, 118.4, 115.7, 110.4, 34.8, 32.9, 31.9; GCLR-MS (EI,
m/z): [M]+ calculated for C25H24O: 340.1; found: 340.1.
2-Benzyl-5-(benzyloxy)-3-phenylbenzofuran (3d): The title compound was prepared using the general
procedure B; Yield: 67 mg (86%); Rf = 0.35 (0.5:95 = EtOAc/n-Hexane); White solid; mp:182-184 oC;
IR (neat): 2985, 2956, 1624, 1512, 1448, 1381, 1332, 1310, 1258, 1175, 1042, 948, 879, 852, 825, 745
cm-1; H NMR (400 MHz, CDCl3): δ, 7.53-7.45 (m, 6H), 7.41 (3H), 7.36-7.31 (4H), 7.28 (d, J = 7.0
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Hz, 3H), 7.18 (d, J = 2.5 Hz, 1H), 6.99 (dd, J = 8.9, 2.5 Hz, 1H), 5.08 (s, 2H), 4.22 (s, 2H); C NMR
(100 MHz, CDCl3): δ 155.3, 153.5, 149.5, 137.9, 137.3, 132.5, 129.2, 129.0, 128.9, 128.6, 128.59,
128.54, 127.9, 127.6, 127.3, 126.6, 118.5, 113.2, 111.6, 104.2, 71.0, 33.0; HR-MS (APCI, m/z):
[M+H]+ calculated for C28H23O2: 391.1698; found: 391.1704.
2-Benzyl-3,5-diphenylbenzofuran (3e):26a The title compound was prepared using the general proce-
o
dure B; Yield: 63 mg (87%); Rf = 0.43 (05:90= EtOAc/n-Hexane); White solid; mp:174-176 C; IR
(neat): 2986, 1621, 1578, 1514, 1451, 1272, 1158, 1062, 1015, 938, 865, 819, 740, cm-1; 1H NMR (400
MHz, CDCl3): δ 7.76 (s, 1H), 7.59 (d, J = 7.2 Hz, 2H)), 7.55 (d, J = 7.0 Hz, 2H), 7.50 (d, J = 7.3 Hz,
4H), 7.42 (t, J = 7.6 Hz, 3H), 7.34-7.28 (m, 6H), 4.23 (s, 2H); 13C NMR (100 MHz, CDCl3): δ 154.0,
153.3, 141.8, 137.8, 136.6, 132.3, 129.2, 129.1, 128.9, 128.7, 128.6, 128.5, 127.5, 127.4, 126.8, 126.6,
123.6, 118.3, 118.5, 111.2, 32.9; GCLR-MS (ESI, m/z): [M]+ calculated for C27H20O: 360.1; found:
360.1.
2-Benzyl-3-phenylbenzofuran-5-carbonitrile (3f): The title compound was prepared using the general
procedure B; Yield: 49 mg (77%); Rf = 0.23 (05:10 = EtOAc/n-Hexane); White solid ; mp:168-170 oC;
IR (neat): 2942, 1615, 1532, 1441, 1229, 1167, 1120, 1035, 1020, 965, 826, 780, 746 cm-1; H NMR
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(400 MHz, CDCl3): δ, 7.76 (s, 1H), 7.57-7.53 (m, 3H), 7.49 (2H), 7.49 (1H), 7.42-7.38 (m, 2H), 7.32
(dd, J = 7.6, 1.2 Hz, 2H), 7.29 (d, J = 6.3 Hz, 2H), 4.23 (s, 2H); 13C NMR (100 MHz, CDCl3): δ, 154.0,
153.3, 141.8, 137.8, 136.6, 132.3, 129.1, 128.9, 128.7, 128.67, 128.5, 127.5, 126.8, 126.6, 123.6, 118.3,
111.2, 32.9; HR-MS (APCI, m/z): [M+H]+ calculated for C22H16NO: 310.1232;found: 310.1229.
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2-Benzyl-5-nitro-3-phenylbenzofuran (3g): The title compound was prepared using the general proce-
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dure B; Yield: 50 mg (76%); Rf = 0.31(05:90 = EtOAc/n-Hexane); Yellow Solid; mp:170-172 C; IR
(neat): 2965, 2775, 2082, 1542, 1456, 1420, 1136, 1123, 1013, 982, 878, 816, 736 cm-1; 1H NMR (400
MHz, CDCl3): δ 7.69 (d, J = 1.8 Hz, 1H), 7.51–7.47 (4H), 7.43-7.39 (m, 1H), 7.36 (dd, J = 8.6, 1.9 Hz,
1H), 7.31-7.29 (3H), 7.25-7.21 (3H), 4.20 (s, 2H); 13C NMR (100 MHz, CDCl3): δ 153.9, 153.1, 137.5,
131.7, 130.7, 129.03, 129.02, 128.7, 128.5, 127.6, 126.8, 126.7, 122.4, 117.9, 115.9, 112.6, 32.9; HR-
MS (APCI, m/z): [M+H]+ calculated for C21H16NO3: 330.1130; found: 330.1132.
2-Benzyl-5-fluoro-3-phenylbenzofuran (3h): The title compound was prepared using the general pro-
o
cedure B; Yield: 47 mg (78%); Rf = 0.42(05:90 = EtOAc/n-Hexane); White Solid; mp:168-170 C; IR
(neat): 2985, 1686, 1542, 1512, 1458, 1345, 1238, 1164, 1087, 1042, 1013, 934, 878, 841, 797, 739 cm-
1
1; H NMR (400 MHz, CDCl3): δ, 7.48 (d, J = 4.4 Hz, 4H), 7.38 (m, 2H), 7.30 (d, J = 7.2 Hz, 2H),
7.26-7.20 (m, 4H), 6.98 (td, J = 9.0, 2.6 Hz, 1H), 4.19 (s, 2H); 13C NMR (100 MHz, CDCl3): δ, 160.6,
158.2, 154.4, 150.5, 137.6, 131.9, 129.5 (d, J = 10.3 Hz), 128.9 (d, J = 4.9 Hz), 128.6 (d, J = 19.1 Hz),
127.5, 126.7, 118.5 (d, J = 3.8 Hz), 111.7, 111.6, 111.4, 105.45 (d, J = 25.4 Hz), 33.0; HR-MS (APCI,
m/z): [M]+ calculated for C21H15FO: 302.1101; found: 302.1126.
2-Benzyl-5-chloro-3-phenylbenzofuran (3i):26a The title compound was prepared using the general
o
procedure B; Yield: 51 mg (80%); Rf = 0.45 (05:95= EtOAc/n-Hexane); White Solid; mp:175-178 C;
IR (neat): 2931, 1599, 1545, 1476, 1439, 1412, 1328, 1259, 1232, 1112, 1084, 1060, 1031, 905, 874,
746 cm-1; 1H NMR (400 MHz, CDCl3): δ, 7.53 (d, J = 2.0 Hz, 1H), 7.48 (d, J = 1.7 Hz, 1H), 7.47 (2H),
7.41-7.34 (m, 3H), 7.29 (d, J = 6.4 Hz, 2H), 7.24-7.20 (m, 4H), 4.19 (s, 2H); 13C NMR (100 MHz,
CDCl3): δ 154.1, 152.7, 137.5, 131.7, 130.1, 129.0, 128.9, 128.7, 128.49, 128.45, 127.6, 126.7, 124.1,
119.4, 118.0, 112.1, 32.9; GCLR-MS (EI, m/z): [M]+ calculated for C21H15ClO: 318.1; found: 318.1.
2-Benzyl-5-bromo-3-phenylbenzofuran (3j):26a The title compound was prepared using the general
o
procedure B; Yield: 55 mg (76%); Rf = 0.43(05:95 = EtOAc/n-Hexane); White Solid; mp:169-171 C;
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IR (neat): 2923, 2093, 1856, 1756, 1486, 1356, 1092, 954, 826, 754 cm-1; H NMR (400 MHz,
CDCl3): δ, 7.69 (d, J= 1.8 Hz, 1H), 7.50 -7.46 (m, 4H), 7.42-7.40 (m, 1H), 7.36 (dd, J = 8.6, 1.9 Hz,
1H), 7.34-7.28 (m, 3H), 7.27-7.22 (m, 3H), 4.20 (s, 2H); 13C NMR (100 MHz, CDCl3): δ, 153.9, 153.1,
137.5, 131.7, 130.7, 129.03, 129.02, 128.7, 128.5, 127.6, 126.8, 126.7, 122.4, 117.9, 115.9, 112.6, 32.9;
GCLR-MS (EI, m/z): [M]+ calculated for C21H15BrO: 362.0; found: 362.0.
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2-Benzyl-5-iodo-3-phenylbenzofuran (3k):26a The title compound was prepared using the general pro-
cedure B; Yield: 65 mg (79%); Rf = 0.38 (05:90 = EtOAc/n-Hexane); White Solid; mp:182-184 ˚C; IR
1
(neat): 2945, 1924, 1826, 1584, 1456, 1258, 1142, 1035, 924, 846, 743 cm-1; H NMR (400 MHz,
CDCl3): δ 7.89 (d, J = 1.6 Hz, 1H), 7.54 (dd, J = 8.6, 1.7 Hz, 1H), 7.48 (d, J= 2.3 Hz, 4H), 7.41-7.38
(m, 1H), 7.30 (2H), 7.24–7.20 (4H), 4.19 (s, 2H); 13C NMR (100 MHz, CDCl3): δ 153.7, 153.5, 137.50
132.5, 131.7, 131.4, 129.07, 129.02, 128.7, 128.6, 128.5, 127.6, 126.7, 117.6, 113.1, 86.3, 32.8; GCLR-
MS (EI, m/z): [M]+ calculated for C21H15IO: 410.0; found: 410.1.
2-Benzyl-5,7-dichloro-3-phenylbenzofuran (3l): The title compound was prepared using the general
procedure B; Yield: 52 mg (74%); Rf = 0.37 (02:98 = EtOAc/n-Hexane); White Solid; mp:165-167 oC;
1
IR (neat): 2926, 1612, 1547, 1520, 1448, 1284, 1032, 867, 801, 792, 759 cm-1; H NMR (400 MHz,
CDCl3): δ 7.57–7.39 (m, 6H), 7.39–7.17 (m, 6H), 4.24 (s, 2H); 13C NMR (100 MHz, CDCl3): δ 155.1,
148.8, 137.1, 131.18, 131.17, 129.07, 129.00, 128.7, 128.6, 128.4, 127.9, 126.8, 124.1, 118.6, 118.1,
117.1, 32.8; HR-MS (APCI, m/z): [M+H]+ calculated for C21H15Cl2O: 353.0494; found: 353.0482.
2-Benzyl-5-bromo-7-chloro-3-phenylbenzofuran (3m): The title compound was prepared using the
general procedure B; Yield: 62 mg (79%); Rf = 0.31 (02:98 = EtOAc/n-Hexane); White Solid; mp:186-
188 oC; IR (neat): 2965, 1612, 1574, 1521, 1450, 1381, 1330, 1257, 1214, 1108, 1048, 1015, 932, 875,
1
759 cm-1; H NMR (400 MHz, CDCl3): δ 7.56 (d, J = 1.7 Hz, 1H), 7.51-7.45 (2H), 7.42 (dd, J = 7.2,
4.3 Hz, 3H), 7.35-7.28 (m, 3H), 7.26-7.23 (m, 3H), 4.20 (s, 2H); 13C NMR (100 MHz, CDCl3): δ
154.9, 149.1, 137.1, 131.7, 131.1, 129.08, 129.02, 128.7, 128.4, 127.9, 126.8, 126.7, 121.1, 118.5,
117.5, 115.6, 32.8; HR-MS (APCI, m/z): [M+H]+ calculated for C21H15BrClO: 396.9989; found:
397.0000.
2-Benzyl-5-chloro-7-methyl-3-phenylbenzofuran (3n): The title compound was prepared using the
general procedure B; Yield: 56 mg (82%); Rf = 0.31(05:95 = EtOAc/n-Hexane); Yellow Solid; mp:185-
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187 oC; IR (neat): 2920, 1625, 1580, 1522, 1451, 1272, 1159, 1049, 1022, 940, 876, 746 cm-1; 1H NMR
(400 MHz, CDCl3): δ 7.47 (4H), 7.41-7.36 (m, 2H), 7.30 (d, J = 7.2 Hz, 2H), 7.25 (d, J = 6.6 Hz, 3H),
7.06 (d, J = 1.0 Hz, 1H), 4.20 (s, 2H), 2.48 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 153.6, 151.7,
137.7, 132.0, 129.4, 129.0, 128.9, 128.6, 128.4, 128.2, 127.5, 126.6, 124.9, 122.7, 118.2, 116.8, 32.9,
14.9; HR-MS (APCI, m/z): [M+H]+ calculated for C22H17ClO: 333.1041; found: 333.1049.
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2,7-Dibenzyl-5-chloro-3-phenylbenzofuran (3o): The title compound was prepared using the general
procedure B; Yield: 68 mg (84%); Rf = 0.38 (0.2:98 = EtOAc/n-Hexane); White Solid; mp:188-190 oC;
1
IR (neat): 2975, 2929, 1642, 1526, 1429, 1398, 1225, 1109, 956, 847, 748 cm-1; H NMR (400 MHz,
CDCl3): δ 7.44 (m, 4H), 7.37 (d, J = 1.9 Hz, 2H), 7.28 (d, J = 7.4 Hz, 2H), 7.26-7.19 (m, 8H), 7.02 (d, J
13
= 1.8 Hz, 1H), 4.18 (s, 2H), 4.16 (s, 2H); C NMR (100 MHz, CDCl3): δ 153.8, 151.1, 139.3, 137.6,
131.9, 129.8, 129.01, 129.00, 128.9, 128.6, 128.56, 128.55, 128.50, 127.5, 126.6, 126.3, 126.1, 124.3,
118.1, 117.5, 35.7, 32.9; HR-MS (APCI, m/z): [M+H]+ calculated for C28H22ClO: 409.1359; found:
409.1329.
2-Benzyl-5-chloro-7-nitro-3-phenylbenzofuran (3p): The title compound was prepared using the gen-
eral procedure B; Yield: 51 mg (70%); Rf = 0.31 (05:95 = EtOAc/n-Hexane); Light Yellow Solid; mp:
o
1
177-180 C; IR (neat): 2921, 2053, 1531, 1461, 1424, 1128, 1110, 1031, 996, 884, 864,746 cm-1; H
NMR (400 MHz, CDCl3): δ 7.56 – 7.50 (3H), 7.48 – 7.46 (m, 2H), 7.45 – 7.43 (3H), 7.34 (m, 2H),
7.30 – 7.26 (m, 2H), 4.24 (s, 2H); 13C NMR (100 MHz, CDCl3): δ 155.1, 148.8, 137.1, 131.18, 131.17,
129.07, 129.00, 128.7, 128.6, 128.4, 127.9, 126.8, 124.1, 118.6, 118.1, 117.1, 32.8; HR-MS (APCI,
m/z): [M+H]+ calculated for C21H15ClNO3: 364.0740; found: 364.0735.
2-Benzyl-5-bromo-7-methoxy-3-phenylbenzofuran (3q): The title compound was prepared using the
general procedure B; Yield: 63 mg (88%); Rf = 0.39 (05:90 = EtOAc/n-Hexane); White Solid; mp:163-
o
164 C; IR (neat): 2923, 1617, 1585, 1442, 1340, 1257, 1218, 1166, 1120, 1070, 1028, 924, 870, 841,
754 cm-1; 1H NMR (400 MHz, CDCl3): δ 7.46-7.44 (3H), 7.38 (m, 1H), 7.31-7.24 (m, 4H), 7.21 (d, J =
7.5 Hz, 3H), 6.90 (d, J = 1.6 Hz, 1H), 4.19 (s, 2H), 3.97 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 153.8,
145.5, 142.5, 137.5, 131.7, 131.6, 129.0, 128.9, 128.6, 128.4, 127.6, 126.6, 118.3, 115.9, 114.9, 110.0,
56.3, 32.8; HR-MS (APCI, m/z): [M+Na]+ calculated for C22H17BrNaO2: 415.0310; found: 415.0283.
2-Benzyl-4,6-dimethyl-3-phenylbenzofuran (3r): The title compound was prepared using the general
procedure B; Yield: 135 mg (86%); Rf = 0.39 (05:90 = EtOAc/n-Hexane); White Solid; mp: 180-182
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oC; IR (neat): 2930, 1612, 1573, 1432, 1338, 1280, 1221, 1148, 1124, 1067, 1015, 932, 853, 812, 751
cm-1; 1H NMR (400 MHz, CDCl3): δ 7.44 – 7.38 (5H), 7.28 – 7.26 (m, 2H), 7.20 – 7.18 (3H), 7.11 (s,
1H), 3.96 (s, 2H), 2.41 (s, 3H), 2.08 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 154.6, 152.3, 138.2,
133.9, 133.8, 130.9, 130.8, 128.5, 128.5, 128.1, 127.4, 126.4, 125.6, 124.9, 118.7, 109.0, 32.6, 21.4,
19.3; HR-MS (APCI, m/z): [M-H]+ calculated for C23H19O: 311.1436; found: 311.1415.
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2-Benzyl-6,7-dimethyl-3-phenylbenzofuran (3s): The title compound was prepared using the general
procedure B; Yield: 130 mg (83%); Rf = 0.37 (05:90 = EtOAc/n-Hexane); White Solid; mp: 176-178
oC; IR (neat): 2930, 1612, 1573, 1432, 1338, 1280, 1221, 1148, 1124, 1067, 1015, 932, 853, 812, 751
1
cm-1; H NMR (400 MHz, CDCl3): δ 7.55 – 7.53 (2H), 7.49 (m, 2H), 7.41 – 7.30 (6H), 7.27 – 7.25
(m, 1H), 7.09 (d, J = 7.9 Hz, 1H), 4.25 (s, 2H), 2.46 (s, 3H), 2.42 (s, 3H); 13C NMR (100 MHz,
CDCl3): δ 153.9, 151.7, 138.3, 132.9, 132.4, 129.0, 128.8, 128.6, 128.5, 127.1, 126.5, 126.0, 124.7,
119.7, 118.5, 116.4, 32.9, 19.2, 11.7; HR-MS (APCI, m/z): [M-H]+ calculated for C23H19O: 311.1436;
found: 311.1424.
2-Benzyl-4,6,7-trimethyl-3-phenylbenzofuran (3t): The title compound was prepared using the gen-
eral procedure B; Yield: 136 mg (84%); Rf = 0.40 (05:90 = EtOAc/n-Hexane); White Solid; mp: 177-
o
180 C; IR (neat): 2930, 1627, 1573, 1432, 1338, 1280, 1221, 1148, 1124, 1067, 1015, 932, 853, 812,
751 cm-1; 1H NMR (400 MHz, CDCl3): δ 7.44 – 7.38 (5H), 7.28 – 7.26 (m, 2H), 7.20 – 7.18 (3H), 7.11
13
(s, 1H), 3.96 (s, 2H), 2.41 (s, 3H), 2.34 (s, 3H), 2.08 (s, 3H); C NMR (100 MHz, CDCl3): δ 153.5,
152.1, 138.4, 134.1, 131.9, 130.8, 128.53, 128.4, 128.0, 127.6, 127.3, 126.3, 126.2, 124.7, 119.1, 117.0,
32.6, 18.9, 11.4 ; HR-MS (APCI, m/z): [M-H]+ calculated for C24H23O: 327.1749; found: 327.1753.
2-Benzyl-7-methoxy-3-phenylbenzofuran-5-ol (3u): The title compound was prepared using the gen-
eral procedure B; Yield: 49 mg (73%); Rf = 0.35 (20:80 = EtOAc/n-Hexane); Yellow solid; mp:164-
166 oC; IR (neat): 2835, 2079, 1644, 1576, 1423, 1266, 1210, 1109, 962, 854, 748 cm-1; 1H NMR (400
MHz, CDCl3): δ 7.53 – 7.4 (4H), 7.39 – 7.37 (1H), 7.31 – 7.22 (5H), 7.14 (s, 1H), 7.01 (s, 1H), 5.54 (s,
1H), 4.19 (s, 2H), 3.91 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 151.6, 148.4, 144.9, 142.7, 138.3,
136.5, 132.7, 128.9, 128.8, 128.6, 128.5, 127.2, 126.5, 121.3, 118.3, 103.8, 94.7, 56.4, 32.9. HR-MS
(APCI, m/z): [M+H]+ calculated for C22H19O3: 331.1329; found: 331.1352.
N-(2-Benzyl-3-phenylbenzofuran-5-yl)acetamide (3v):26c The title compound was prepared using the
general procedure B; Yield: 47 mg (68%); Rf = 0.30 (50:50 = EtOAc/n-Hexane); Brown solid; mp:176-
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178 C; IR (neat): 3326, 2935, 2841, 1426, 1136, 1048, 959, 847, 752 cm-1; H NMR (400 MHz,
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CDCl3): δ 7.72 (d, J = 4.0 Hz, 1H), 7.48 – 7.42 (4H), 7.37 – 7.27 (6H), 7.25 – 7.23(2H), 4.18 (s,2H),
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2.13 (s, 3H); C NMR (100 MHz, CDCl3): δ 168.4, 151.5, 137.8, 133.1, 132.2, 129.1, 129.1, 128.9,
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128.7, 128.5, 127.4, 126.6, 118.9, 118.5, 117.7, 112.1, 111.2, 32.9, 24.4; GCLR-MS (EI, m/z): [M]+
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calculated for C23H19NO2: 341.1; found: 341.1.
5-Methyl-2-(4-methylbenzyl)-3-(p-tolyl)benzofuran (5a): The title compound was prepared using the
general procedure B; Yield: 56 mg (86%); Rf = 0.42(02:98 = EtOAc/n-Hexane); White Solid; mp:184-
186 oC; IR (neat): 2920, 2092, 1637, 1421, 1353, 1223, 1114, 1024, 954, 882, 823, 748 cm-1; 1H NMR
(400 MHz, CDCl3): δ 7.44 (d, J = 8.0 Hz, 2H), 7.39 (s, 1H), 7.35 (d, J = 8.3 Hz, 1H), 7.31 (d, J = 7.9
Hz, 2H), 7.17 (d, J = 8.1 Hz, 2H), 7.14-7.07 (m, 3H), 4.17 (s, 2H), 2.45 (s, 6H), 2.34 (s, 3H); 13C NMR
(100 MHz, CDCl3): δ 152.7, 136.9, 136.0, 135.0, 132.0, 129.7, 129.5, 129.3, 129.0, 128.9, 128.4,
125.0, 119.6, 118.4, 117.8, 110.6, 32.5, 21.4, 21.3, 21.0; HR-MS (APCI, m/z): [M-H]+ calculated for
C24H21O: 325.1587; found: 325.1580.
2-(4-Fluorobenzyl)-3-(4-fluorophenyl)-5-methylbenzofuran (5b): The title compound was prepared
using the general procedure B; Yield: 53 mg (79%); Rf = 0.45 (02:98 = EtOAc/n-Hexane); White Solid;
o
1
mp:175-177 C; IR (neat): 2923, 2092, 1646, 1484, 1353, 1256, 1124, 1088, 1009, 826, 742cm-1; H
NMR (400 MHz, CDCl3): δ 7.42 (dd, J = 8.6, 5.4 Hz, 2H), 7.32 (d, J = 8.4 Hz, 1H), 7.29 (s, 1H), 7.16
(dd, J = 11.2, 6.2 Hz, 4H), 7.09 (d, J = 8.3 Hz, 1H), 6.96 (t, J = 8.7 Hz, 2H), 4.11 (s, 2), 2.41 (s, 3H);
13C NMR (100 MHz, CDCl3): δ 163.1 (d, J = 46.4 Hz), 160.7 (d, J = 44.5 Hz), 152.6, 152.4, 133.4 (d,
J = 3.4 Hz), 132.4, 130.6 (d, J = 8.0 Hz), 129.9 (d, J = 8.0 Hz), 128.6, 128.4 (d, J = 3.4 Hz), 125.3,
119.3, 117.1, 115.8 (d, J = 21.5 Hz), 115.5 (d, J = 21.4 Hz), 110.6, 32.0, 21.3; HR-MS (ESI, m/z): [M-
H]+ calculated for C22H15F2O: 333.1085; found: 333.1081.
2-(4-Chlorobenzyl)-3-(4-chlorophenyl)-5-methylbenzofuran (5c): The title compound was prepared
using the general procedure B; Yield: 62 mg (84%); Rf = 0.43 (02:98 = EtOAc/n-Hexane); White Solid;
o
mp: 178-180 C; IR (neat): 2956, 1629, 1569, 1512, 1439, 1328, 1238, 1112, 1051, 1031, 1121, 926,
875, 843, 797,cm-1; 1H NMR (400 MHz, CDCl3): δ 7.44 (d, J = 8.5 Hz, 2H), 7.38 (d, J = 8.5 Hz, 2H),
7.32 (d, J = 8.4 Hz, 1H), 7.29 (s, 1H), 7.24 (2H), 7.13 (d, J = 8.4 Hz, 2H), 7.09 (dd, J = 8.4, 1.2 Hz, 1H),
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4.11 (s, 2H), 2.41 (s, 3H); C NMR (100 MHz, CDCl3): δ 152.7, 152.2, 136.1, 133.3, 132.5, 130.9,
130.3, 130.2, 129.7, 129.1, 128.7, 128.3, 125.5, 119.3, 117.2, 110.7, 32.2, 21.3; HR-MS (APCI, m/z):
[M-H]+ calculated for C22H15Cl2O: 365.0494; found: 365.0486.
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2-(4-Bromobenzyl)-3-(4-bromophenyl)-5-methylbenzofuran (5d): The title compound was prepared
using the general procedure B; Yield: 73 mg (81%); Rf = 0.44 (02:98 = EtOAc/n-Hexane); White Solid;
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o
mp: 188-190 C; IR (neat): 2923, 2082, 1634, 1527, 1479, 1385, 1260, 1128, 1065, 1034, 1019, 986,
826, 745 cm-1; 1H NMR (400 MHz, CDCl3): δ 7.59 (d, J = 8.4 Hz, 2H), 7.40 (d, J = 8.4 Hz, 2H), 7.34–
7.28 (4H), 7.09 (dd, J = 10.0, 4.7 Hz, 3H), 4.09 (s, 2H), 2.41 (s, 3H); 13C NMR (100 MHz, CDCl3): δ
152.7, 152.0, 136.6, 132.5, 132.0, 131.7, 131.3, 130.6, 130.1, 128.2, 125.5, 121.4, 120.5, 119.3, 117.2,
110.7, 32.3, 21.3; HR-MS (APCI, m/z): [M-H]+ calculated for C22H15Br2O: 452.9484; found:
452.9474.
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3-([1,1'-Biphenyl]-4-yl)-2-([1,1'-biphenyl]-4-ylmethyl)-5-methylbenzofuran (5e): The title com-
pound was prepared using the general procedure B; Yield: 72 mg (80%); Rf = 0.4 (05:95 = EtOAc/n-
Hexane); White solid; mp:198-200oC; IR (neat): 2938, 1982, 1645, 1532, 1465, 1383, 1274, 1108,
1049, 1014, 986, 843, 748 cm-1; 1H NMR (400 MHz, CDCl3) δ 7.73 (d, J = 8.0 Hz, 2H), 7.67 (m, 2H),
7.62 – 7.53 (6H), 7.50 – 7.53 (10H), 7.12 (dd, J = 8.0, 4.0 Hz, 1H), 4.29 (s, 2H), 2.46 (s, 3H); 13C NMR
(100 MHz, CDCl3): δ 152.8, 152.7, 140.9, 140.7, 140.1, 139.6, 137.0, 132.3, 131.6, 129.5, 128.9,
128.9, 128.8, 128.7, 128.6, 127.5, 127.4, 127.2, 127.1, 127.0, 125.3, 119.6, 117.8, 110.7, 32.7, 21.4;
HR-MS (APCI, m/z): [M-H]+ calculated for C34H25O: 449.1900; found: 449.1903.
5-Methyl-3-(naphthalen-1-yl)-2-(naphthalen-1-ylmethyl)benzofuran (5f): The title compound was
prepared using the general procedure B; Yield: 60 mg (76%); Rf = 0.42 (02:98 = EtOAc/n-Hexane);
o
White solid; mp 186-188 C; IR (neat): 2907, 1974, 1651, 1524, 1452, 1387, 1265, 1098, 1053, 1031,
965, 850, 746 cm-1; 1H NMR (400 MHz, CDCl3): δ 8.05 – 8.03 (m, 2H), 7.88 – 7.86 (m, 2H), 7.79 (d,
J = 8.0 Hz, 2H), 7.49 – 7.46 (4H), 7.43 – 7.40(3H), 7.29 (d, J = 8.0 Hz, 1H), 7.17 (s, 1H), 7.00 (dd, J =
8.0, 4.0 Hz, 1H), 6.15 (d, J = 4.0 Hz, 1H), 4.53 (s, 2H), 2.38 (s, 3H) ; 13C NMR (100 MHz, CDCl3): δ
157.6, 153.2, 133.9, 133.2, 131.9, 131.7, 131.1, 128.9, 128.7, 128.5, 127.7, 127.5, 127.3, 127.1, 126.4,
126.1, 125.9, 125.9, 125.7, 125.3, 125.1, 124.5, 124.1, 123.9, 121.0, 120.3, 110.3, 103.5, 32.5, 21.3;
HR-MS (APCI, m/z): [M]+ calculated for C30H22O: 398.1665; found: 398.1663.
5-Methyl-3-(thiophen-2-yl)-2-(thiophen-3-yl)benzofuran (5g): The title compound was prepared us-
ing the general procedure B; Yield: 40 mg (67%); Rf = 0.45 (05:95 = EtOAc/n-Hexane); Yellow white
o
solid; mp: 156-158 C; IR (neat):2965, 1584, 1513, 1450, 1375, 1322, 1020, 934, 831, 802, 781, 767,
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748 cm-1; 1H NMR (400 MHz, CDCl3): δ 7.54 (m, 2H), 7.51 – 7.47 (2H), 7.41 (d, J = 8.0 Hz, 1H), 7.38
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– 7.33 (m, 2H), 7.27 (1H), 7.12 (d, J = 8.0 Hz, 1H), 4.23 (s, 2H), 2.46 (s, 3H); C NMR (100 MHz,
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CDCl3): δ 152.8, 152.6, 132.7, 132.2, 129.2, 128.9, 128.8, 128.8, 128.6, 128.5, 127.3, 126.7, 125.2,
119.6, 118.1, 110.8, 32.9, 21.4; HR-MS (APCI, m/z): [M-H]+ calculated for C18H13OS2: 309.0402;
found: 309.0405.
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2-Benzyl-5-methylbenzofuran (5h): The title compound was prepared using the general procedure B;
Yield: 38 mg (84%); Rf = 0.45 (02:98 = EtOAc/n-Hexane); Light Yellow liquid; IR (neat): 2935, 1642,
1536, 1503, 1449, 1325, 1281, 1123, 972, 856, 741 cm-1; 1H NMR (400 MHz, CDCl3): δ 7.37-7.22 (m,
7H), 7.02 (d, J = 8.2 Hz, 1H), 6.30 (s, 1H), 4.09 (s, 2H), 2.41 (s, 3H); 13C NMR (100 MHz, CDCl3): δ
157.8, 153.4, 137.3, 131.9, 128.9, 128.9, 128.6, 126.7, 124.6, 120.3, 110.4, 103.1, 35.0, 21.3; GCLR-
MS (EI, m/z): [M]+ calculated for C16H14O: 222.1; found: 222.1.
2-Benzyl-5-methoxybenzofuran (5i):27 The title compound was prepared using the general procedure
B; Yield: 39 mg (83%); Rf = 0.35 (10:90 = EtOAc/n-Hexane) ; Light Yellow liquid; IR (neat): 2962,
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1628, 1537, 1497, 1436, 1357, 1242, 1132, 1083, 949, 845, 752 cm-1; H NMR (400 MHz, CDCl3): δ
7.34 – 7.26 (6H), 6.94 (d, J = 4.0 Hz, 1H), 6.81 (dd, J = 8.0, 4.0 Hz, 1H), 6.31 (s, 1H), 4.08 (s, 2H), 3.81
(s, 3H); 13C NMR (100 MHz, CDCl3): δ 158.7, 155.8, 149.9, 137.3, 129.4, 128.9, 128.6, 126.7, 111.8,
111.3, 103.5, 103.3, 55.9, 35.1; GCLR-MS (EI, m/z): [M]+ calculated for C16H14O2: 238.0; found:
238.0.
2-Benzyl-3,5-dimethylbenzofuran (5j): The title compound was prepared using the general procedure
B; Yield: 35 mg (74%); Rf = 0.38 (5:95 = EtOAc/n-Hexane) ; Light Yellow liquid; IR (neat): 3025,
2965, 1623, 1510, 1450, 1285, 1125, 1042, 972, 856, 745 cm-1; 1H NMR (400 MHz, CDCl3): δ 7.39 –
7.29 (7H), 7.11 (dd, J = 8.0, 4.0 Hz, 1H), 4.15 (s, 2H), 2.53 (s, 2H), 2.28 (s, 3H); 13C NMR (100 MHz,
CDCl3): δ 152.6, 152.3, 138.2, 131.5, 130.4, 128.6, 128.6, 126.5, 124.7, 118.9, 110.6, 110.4, 32.7, 21.5,
8.1; HR-MS (APCI, m/z): [M+H]+ calculated for C17H17O: 237.1274; found: 237.1258.
2-Benzyl-5-methoxy-3-methylbenzofuran (5k): The title compound was prepared using the general
procedure B; Yield: 41 mg (81%); Rf = 0.37 (5:95 = EtOAc/n-Hexane) ; Light Yellow liquid; IR (neat):
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2975, 1628, 1512, 1465, 1279, 1134, 1027, 976, 848, 760cm-1; H NMR (400 MHz, CDCl3): δ 7.40 –
7.28 (6H), 7.02 (d, J = 4.0 Hz, 1H), 6.92 (dd, J = 8.0, 4.0 Hz, 1H), 4.15 (s, 2H), 3.92 (s, 3H), 2.29 (s,
3H); 13C NMR (100 MHz, CDCl3): δ 155.8, 153.2, 149.1, 138.1, 130.9, 128.7, 128.6, 126.6, 111.8,
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111.3, 111.0, 102.0, 56.0, 32.8, 8.2; HR-MS (APCI, m/z): [M+H]+ calculated for C17H17O2: 253.1229;
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2-(Furan-2-ylmethyl)-3,5-dimethylbenzofuran (5l): The title compound was prepared using the gen-
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eral procedure B; Yield: 97 mg (86%); Rf = 0.36 (5:95 = EtOAc/n-Hexane) ; Light red liquid; IR (neat):
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3025, 2965, 1623, 1510, 1450, 1285, 1125, 1042, 972, 856, 745 cm-1; H NMR (400 MHz, CDCl3): δ
7.39 – 7.37 (1H), 7.35 (m, 1H), 7.33 – 7.27 (m, 3H), 7.11 (d, J = 8.0 Hz, 1H), 4.15 (s, 2H), 2.53 (s, 3H),
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2.28 (s, 3H); C NMR (100 MHz, CDCl3): δ 153.5, 152.4, 139.2, 131.5, 130.8, 129.7, 128.5, 126.5,
124.7, 118.9, 110.6, 110.4, 32.7, 21.5, 8.2; HR-MS (APCI, m/z): [M-H]+ calculated for C15H13O2:
225.0916; found: 225.0923.
2-((3,5-Dimethylbenzofuran-2-yl)methyl)-1-methyl-1H-pyrrole (5m): The title compound was pre-
pared using the general procedure B; Yield: 92 mg (77%); Rf = 0.33 (10:90 = EtOAc/n-Hexane) ; Light
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Yellow liquid; IR (neat): 2872, 2532, 1986, 1854, 1723, 1458, 1238, 1132, 960, 852, 752, cm-1; H
NMR (400 MHz, CDCl3): δ 8.37 – 8.35 (m, 1H), 7.44 (1H), 7.35 – 7.31 (3H), 7.28 – 7.26 (1H), 7.05
(m, 1H), 4.08 (s, 2H), 3.64 (s, 3H), 2.48 (s, 36H), 2.22 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 152.3,
128.6, 128.4, 126.5, 124.8, 124.1, 122.9, 121.8, 119.1, 117.9, 110., 110.0, 33.4, 32.6, 21.4, 8.7; HR-MS
(APCI, m/z): [M+H]+ calculated for C16H18NO: 240.1388; found: 240.1392.
3-((3,5-Dimethylbenzofuran-2-yl)methyl)-1-methyl-1H-indole (5n): The title compound was pre-
pared using the general procedure B; Yield: 103 mg (72%); Rf = 0.38 (10:90 = EtOAc/n-Hexane) ;
Light Yellow liquid; IR (neat): 2995, 2612, 2076, 1846, 1735, 1484, 1238, 1036, 954, 835, 760, cm-1;
1H NMR (400 MHz, CDCl3): δ 8.37 – 8.35 (m, 1H), 7.43 (s, 1H), 7.35 – 7.33 (m, 2H), 7.32 – 7.29 (m,
1H), 7.27 – 7.25 (2H), 7.06 (s, 1H), 4.08 (s, 2H), 3.65 (s, 3H), 2.48 (s, 3H), 2.22 (s, 3H); 13C NMR (100
MHz, CDCl3): δ 152.5, 152.4, 139.6, 138.2, 137.9, 131.5, 130.4, 128.6, 128.6, 126.5, 125.2, 124.7,
124.0, 122.9, 121.9, 119.0, 117.9, 33.4, 32.6, 21.4, 8.1; HR-MS (APCI, m/z): [M+H]+ calculated for
C20H20NO: 290.1545; found: 290.1537.
2-Benzyl-3-cyclohexyl-5-methylbenzofuran (5o): The title compound was prepared using the general
procedure B; Yield: 35 mg (66%); Rf = 0.30 (5:95 = EtOAc/n-Hexane) ; Light Yellow liquid; IR (neat):
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2965, 2512, 2084, 1641, 1456, 1130, 1032, 910, 835, 758, 744 cm-1; H NMR (400 MHz, CDCl3): δ
7.43 (s, 1H), 7.29 – 7.25 (3H), 7.21 (m, 3H), 6.99 (dd, J = 8.0, 4.0 Hz, 1H), 4.10 (s, 2H), 2.72 (m, 1H),
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2.44 (s, 3H), 1.88 – 1.78 (7H), 1.40 – 1.35 (3H); 13C NMR (100 MHz, CDCl3): δ 152.8, 151.1, 138.3,
131.1, 129.4, 128.5, 128.4, 126.4, 124.2, 120.4, 120.3, 110.6, 36.0, 32.9, 32.6, 26.9, 26.2, 21.5; HR-MS
(APCI, m/z): [M-H]+ calculated for C22H23O: 303.1743; found: 303.1755.
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5-Methyl-2-(naphthalen-1-ylmethyl)benzofuran (5p): The title compound was prepared using the
general procedure B; Yield: 42 mg (77%); Rf = 0.35 (10:90 = EtOAc/n-Hexane) ; Light Yellow liquid;
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IR (neat): 2969, 1633, 1579, 1563, 1457, 1341, 1262, 1113, 1077, 1027, 938, 851, 762 cm-1; H NMR
(400 MHz, CDCl3): δ 7.82– 7.78 (3H), 7.73 (s, 1H), 7.47 – 7.44 (m, 2H), 7.42 (dd, J = 8.0, 4.0 Hz, 1H),
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7.27 (m, 2H), 7.01 (dd, J = 8.0, 4.0 Hz, 1H), 6.33 (d, J = 4.0 Hz, 1H), 4.25 (s, 2H), 2.41 (s, 3H); C
NMR (100 MHz, CDCl3): δ 157.7, 153.4, 134.8, 133.6, 132.4, 131.9, 128.9, 128.2, 127.7, 127.6, 127.3,
127.3, 126.1, 125.6, 124.65 120.3, 110.4, 103.4, 35.2, 21.3; HR-MS (APCI, m/z): [M-H]+ calculated
for C20H15O: 271.1117; found: 271.1121.
3-(2-Benzyl-5-methoxybenzofuran-3-yl)propanenitrile (5q): The title compound was prepared using
the general procedure B; Yield: 70 mg (51%); Rf = 0.20 (20:80 = EtOAc/n-Hexane) ; Yellow solid; mp:
o
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110-112 C; IR (neat): 2894, 1754, 1632, 1557, 1465, 1421, 1235, 1145, 1028, 926, 848, 776 cm-1; H
NMR (400 MHz, CDCl3): δ 7.33-7.29 (3H), 7.26-7.23 (3H), 6.99 (d, J = 4.0 Hz, 1H), 6.87 (dd, J = 8.0,
4.0 Hz, 1H), 4.13 (s, 2H), 3.84 (s, 3H), 3.60 (s, 2H); 13C NMR (100 MHz, CDCl3): δ 156.8, 154.9,
148.9, 136.3, 128.9, 128.5, 128.1, 127.0, 116.6, 113.2, 111.8, 104.9, 101.2, 56.0, 33.0, 12.6; HR-MS
(APCI, m/z): [M+H]+ calculated for C18H15NO2: 278.1181; found: 278.1164.
2-Benzyl-3-(4-(2-bromoethoxy)phenyl)-5-methoxybenzofuran (5r): The title compound was pre-
pared using the general procedure B; Yield: 102 mg (43%); Rf = 0.35 (10:90 = EtOAc/n-Hexane) ;
Brown solid; mp: 146-148 oC; IR (neat): 2975, 2835, 1814, 1630, 1560, 1423, 1356, 1225, 1142, 1009,
938, 878, 754 cm-1; 1H NMR (400 MHz, CDCl3): δ 7.40 (d, J = 4.0 Hz, 2H), 7.35-7.33 (m, 1H), 7.32-
7.30 (5H), 7.29-7.28 (1H), 7.20-7.18 (2H), 6.88 (d, J = 4.0 Hz, 1H), 4.33 (t, J = 4.0 Hz, 2H), 4.11 (s,
2H), 3.84 (s, 3H), 3.68 (t, J = 4.0 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 164.8, 156.2, 151.8, 145.7,
137.1, 131.8, 128.9, 128.8, 128.5, 113.6, 112.7, 105.6, 68.3, 55.6, 33.3, 29.3; HR-MS (APCI, m/z):
[M+H]+ calculated for C24H22BrO3: 437.0752; found: 437.0746.
5-Methoxy-2-methylbenzofuran (5s):26b The title compound was prepared using the general procedure
B; Yield: 28 mg (86%); Rf = 0.42 (05:90 = EtOAc/n-Hexane); Light Yellow liquid; IR (neat): 2856,
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