Traceless OH-Directed Wacker Oxidation-Elimination, an Alternative to Wittig Olefination/Aldol Condensation: One-Pot Synthesis of α,β-Unsaturated and Nonconjugated Ketones from Homoallyl Alcohols

Article abstract of DOI:10.1021/acs.joc.6b01899

A new method for one-pot synthesis of β-substituted and β,β-disubstituted α,β-unsaturated methyl ketones from homoallyl alcohols by sequential PdCl₂/CrO₃-promoted Wacker process followed by an acid-mediated dehydration reaction has been developed. Remarkably, internal homoallyl alcohols delivered regioselectively nonconjugated unsaturated carbonyl compounds under the same protocol. A new starting material-based synthesis of α,β-unsaturated and nonconjugated methyl ketones is demonstrated.

Full text of DOI:10.1021/acs.joc.6b01899

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Article
Traceless OH-directed Wacker Oxidation-Elimination, an Alternative
to Wittig Olefination/Aldol Condensation: One-pot Synthesis of #,#-
Unsaturated and Non-conjugated Ketones from Homoallyl Alcohols
Venkati Bethi, and Rodney Agustinho Fernandes
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b01899 • Publication Date (Web): 26 Aug 2016
Downloaded from http://pubs.acs.org on August 28, 2016
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Traceless OH-directed Wacker Oxidation-Elimination, an
Alternative to Wittig Olefination/Aldol Condensation: One-pot
Synthesis of α,β-Unsaturated and Non-conjugated Ketones from
Homoallyl Alcohols
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Venkati Bethi and Rodney A. Fernandes*
Department of Chemistry, Indian Institute of Technology Bombay
Powai, Mumbai 400076, Maharashtra, India
E-mail: rfernand@chem.iitb.ac.in
ABSTRACT: A new method for one-pot synthesis of β-substituted and β,β-disubstituted α,β-
unsaturated methyl ketones from homoallyl alcohols by sequential PdCl2/CrO3 promoted
Wacker process followed by acid-mediated dehydration reaction has been developed.
Remarkably internal homoallyl alcohols delivered regioselectively non-conjugated unsaturated
carbonyl compounds under the same protocol. A new starting material based synthesis of α,β-
unsaturated and non-conjugated methyl ketones is demonstrated.
INTRODUCTION
The potential applications of α,β-unsaturated ketones are realized in various reactions in the
main stream of organic synthesis, such as Michael addition,1 cycloaddition,2 cyclopropanation,3
epoxidation,4 hydrogenation,5 Morita-Baylis-Hillman reaction,6 etc. Similarly, β,γ-unsaturated
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carbonyl compounds are potential intermediates in synthetic chemistry as well as in
photochemical reactions.7,8
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The classical methods of Wittig,9 Horner–Wadsworth–Emmons10 and Petersen olefination,11
though widely used for the synthesis of α,β-unsaturated ketones, they lead to stoichiometric P
and Si by-products, require sensitive reaction conditions and have low atom economy. The
traditional approach by Claisen-Schmidt condensation of aldehydes and ketones12 by using
stoichiometric base, sometimes leads to a mixture of self-condensed ketone and Michael
addition products. Mukaiyama aldol reaction followed by subsequent dehydration catalyzed by
a Lewis acid13 or the Yanagisawa protocol of condensation of aldehydes with alkenyl
trichloroacetates catalyzed by dibutyltin dimethoxide14 are useful alternatives.
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To overcome the difficulties associated with classical methods, a number of catalytic
processes have been developed.15 Similarly, the one-pot synthesis of enones from various
starting materials has drawn a great attention. Over the last decade, organic chemists have taken
major turn towards developing one-pot methods to avoid purification processes, minimise cost
and waste production.16 A representative example established by Pawluć and co-workers,
demonstrates the highly stereoselective synthesis of (E)-styryl ketones via vinyl silanes from
the readily available styrenes.17 The Au-catalyzed, Meyer-Schuster rearrangement of
propargylic alcohols with small quantities of protic solvent to enones by Sheppard and co-
workers is another notable example.18 Recently, Sugiura and co-workers developed a one-pot
synthesis of β,β-disubstituted α,β-unsaturated carbonyl compounds via TiCl4 promoted aldol
reaction of ketones followed by base induced elimination.19 The cross-metathesis approach
from olefins and vinyl ketones is also an efficient alternative.15a Wang and co-workers
transformed simple terminal olefins into α,β-unsaturated methyl ketones via Wacker-type
oxidation and dehydrogenation sequence using Pd(OAc)2 as catalyst and molecular oxygen
(O2) as a sole oxidant.15e
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The syntheses of β,γ-unsaturated carbonyl compounds are well documented in the literature.
The addition of allylic organometallic reagents with acyl halides is an important example.20 In
addition, the cross-coupling of allylic trifluoroacetates with acylsilanes/stannanes are also
reported.21 A series of β,γ-unsaturated carbonyl compounds were synthesized by cerium-
mediated addition of organolithiums to silylated enaminones,22 Ru-H catalyzed addition of
aldehydes to dienes23 and acid-catalyzed opening of (1-hydroxyalkyl)-1-alkylcyclopropanols.24
Recently, Trofimov and co-workers reported base-catalyzed stereoselective vinylation of
ketones with arylacetylenes to deliver β,γ-unsaturated carbonyl compounds.25a Later, the same
group employed superbase (KOtBu) to synthesize β,γ-unsaturated carbonyl compounds with
excellent stereoselectivity.25b
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We recently developed new alternatives to the well-known Wacker oxidation of terminal
olefins to methyl ketones using Pd-catalyst and various oxidants such as CrO3,26a
Fe2(SO4)3.nH2O26b or DMP.26c When a similar oxidation of aryl homoallyl alcohol was
investigated (using the catalytic system as in ref. 26a), we observed the Wacker oxidation-
elimination product, α,β-unsaturated methyl ketone (Scheme 1). When the reaction was
assisted by addition of acids, the major product was α,β-unsaturated ketone. This method is
substrate selective in delivering the conjugated methyl ketones and deconjugated carbonyl
compounds with high regio- and stereoselectivity. Terminal homoallyl alcohols delivered the
conjugated methyl ketones whereas internal homoallyl alcohols gave deconjugated carbonyl
compounds. A remarkable OH-directed regioselective Wacker oxidation was observed. We
consider this method to have advantages for the synthesis of conjugated/deconjugated carbonyl
compounds from a different starting material and also to be able to overcome some of the
disadvantages of classical condensation methods. The requirement of cheap CrO3 (0.5 equiv)
as oxidant (having good water solubility) and no dry conditions, makes this method
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operationally simple. The exclusive delivery of E-double bonds for noncyclic compounds is
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also a notable feature.
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Scheme 1. Synthesis of α,β-unsaturated and non-conjugated ketones.
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RESULTS AND DISCUSSION
We initiated our studies by choosing homoallyl alcohol 1a as a model substrate to optimize
the reaction conditions (Table 1). Based on our previous report,26a we carried out the reaction
of 1a using PdCl2 (10 mol%), CrO3 (1.5 equiv) in CH3CN/H2O (7:1) at 60 ºC for 3 h. The
desired product, α,β-unsaturated methyl ketone 2a was formed in 12% yield along with β-
hydroxy methyl ketone 3 in 60% yield (Table 1, entry 1). The reaction without PdCl2 resulted
in oxidation of 1a to the corresponding ketone (1-phenyl-3-buten-1-one), obtained in 65% yield
(entry 2). The desired product 2a was assumed to be generated from 3, mediated by the acidic
nature of CrO3. The reaction without the use of CrO3 delivered no product (entry 3). Lowering
the concentration of CrO3 (0.5 equiv) gave 3 in 71% yield (entry 4) with no trace of 2a. An
increase in CrO3 concentration (3.0 equiv) resulted in increased yield of 2a to 22% (entry 5).
This indicated the need of excess CrO3 to effect both Wacker oxidation and the β-hydroxy
elimination. A reaction at higher temperature (100 C) resulted in decomposition and lowered
the yield of 2a (16%, entry 6). We expected that addition of a protic acid would facilitate the
elimination process after Wacker oxidation in the one-pot process. Thus the reaction of 1a
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using PdCl2 (10 mol%), CrO3 (1.5 equiv) in CH3CN/H2O (7:1) at 60 ºC was run for 3 h, during
which the starting material was consumed (TLC monitoring). In the same vessel, we added
CH3COOH (2.0 equiv) and stirred for another 12 h. The desired product 2a was now obtained
in increased yield of 30% (entry 7). Encouraged by this result, we screened a series of acids
with PdCl2 (10 mol%), CrO3 (1.5 equiv) in CH3CN/H2O (7:1) at 60 ºC. Strong acids such as
H3PO4, HNO3, H2SO4, HCl and oxalic acid were employed in the one-pot dehydration process
(entries 8-12). Among these, to our delight, HCl worked well resulting in higher yield of 2a
(57%, entry 11). An increase in amount of HCl (3.0 and 4.0 equiv, entries 13 and 14) gave
exclusive formation of 2a in 75% yield (entry 14). Lowering the Pd-catalyst loading to 5 mol%,
lowered the yield of 2a (57%, entry 15). Lowering of CrO3 concentration (1.0 and 0.5 equiv,
entries 16 and 17) also worked well giving 2a in 74% and 72% yields respectively. A change
in Pd-catalyst to Pd(OAc)2, Pd(dba)2 or Pd(PPh3)4, did not improve the yields (entries 18-20).
In all cases there was exclusive formation of E-olefin bond.
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Table 1. Optimization of reaction conditions to access α,β-unsaturated methyl ketones.a
Entry
Pd-cat.
(mol%)
CrO3
Acid
Time
(h)
Yield of 3
Yield of 2a
(equiv)
(equiv)
(%)
(%)
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PdCl2 (10)
-
1.5
1.5
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PdCl2 (10)
PdCl2 (10)
PdCl2 (10)
PdCl2 (10)
PdCl2 (10)
PdCl2 (10)
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-
0.5
3.0
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1.5
1.5
-
6
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16c
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3
CH3CO2H (2)
H3PO4 (2)
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PdCl2 (10)
PdCl2 (10)
PdCl2 (10)
PdCl2 (10)
PdCl2 (10)
PdCl2 (10)
PdCl2 (5)
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1
HNO3 (2)
H2SO4 (2)
HCl (2)
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Oxalic acid (2)
HCl (3)
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HCl (4)
4
-
HCl (4)
6
-
PdCl2 (10)
PdCl2 (10)
Pd(OAc)2 (10)
Pd(dba)2 (10)
Pd(Ph3P)4 (10)
HCl (4)
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-
0.5
0.5
0.5
0.5
HCl (4)
-
HCl (4)
-
HCl (4)
-
HCl (4)
-
aAll reactions were performed with allyl alcohol 1a (0.5 mmol), Pd-cat. (5-10 mol%), oxidant (0.5 to 1.5 equiv),
acid (2.0-4.0 equiv), at 60 ºC in CH3CN/H2O (7:1). 1-Phenyl-3-buten-1-one (65%), cReaction at 100 °C.
b
With the optimized conditions (Table 1, entry 17 with lower loading of CrO3) the scope of
the reaction was investigated by varying the aryl part of allyl alcohol (Scheme 2). Various aryl
substituted secondary homoallyl alcohols (1a-r) regardless of electron donating or electron
withdrawing ability of substitutions on the aryl ring reacted under the optimized conditions to
afford the corresponding β-substituted, α,β-unsaturated methyl ketones in good yields (2a-r,
Scheme 2). Thus NO2, OMe, Me or OR group containing compounds reacted well giving 2b-l
respectively, under the optimized conditions. The halide-containing compounds, 1m-o were
well-tolerated providing 2m-o respectively, under PdCl2 catalysis. Similarly, free phenolic OH
group did not pose any difficulty in the reaction giving the products in good yields (2p-r)
without the need of any OH group protection. The exclusive delivery of E-olefins is another
notable feature in this transformation.
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Scheme 2: One-pot conversion of secondary homoallyl alcohols to β-substituted α,β-
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unsaturated methyl ketones
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It is difficult to synthesize β,β-disubstituted, α,β-unsaturated methyl ketones via conventional
methods as these suffer from lower reactivity of ketones, generation of self or cross-aldol
and/or Michael addition products. To demonstrate the generality of our protocol we explored
the scope of tertiary homoallyl alcohols to access β,β-disubstituted α,β-unsaturated methyl
ketones (Scheme 3). Tertiary homoallyl alcohols (3a-e) with alkyl or aryl groups were
smoothly converted into the corresponding β,β-disubstituted α,β-unsaturated methyl ketones
(4a-e) in good yields (55-75%, Scheme 3). Homoallyl alcohol 3f with both phenyl groups
afforded 4f in moderate 42% yield. Interestingly, fluorenyl homoallyl alcohol under this
protocol gave 4g in good yield of 62%.
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Scheme 3: One-pot conversion of tertiary homoallyl alcohols to β,β-disubstituted α,β-
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unsaturated methyl ketones
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To extend the scope of this reaction we tested selected tertiary homoallyl alcohols under the
standard conditions (Table 2). Thus the reaction of internal olefin based tertiary homoallyl
alcohol 5a delivered regioselectively ,-disubstituted β,-unsaturated ketone 6a in 63% yield
(entry 1). We did not detect the other possible regioisomer or olefin isomerized product. The
reaction displayed an excellent hydroxyl-directed regioselective Wacker oxidation, hydroxyl
elimination and remarkably no isomerization of the more substituted double bond. It is worth
mentioning that the synthesis of such non-conjugated unsaturated carbonyl compounds would
be quite a challenging task.27 Similarly, the reaction of other representative internal olefin based
tertiaryhomoallyl alcohols 5b-e delivered corresponding β,γ-unsaturated carbonyl compounds
6b-e in good yields (entries 2-5). The cycloalkane based terminal homoallylic alcohols 5f-h
also delivered the β,γ-unsaturated methyl ketones 6f-h in good yields (entries 6-8). The last
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case gave a mixture of β,- and α,β-unsaturated methyl ketones 6h and 6h' in 0.7:1 ratio (entry
8). The internal olefin based cyclohexane derived tertiaryhomoallyl alcohols 5i and j delivered
corresponding ,-unsaturated ketones 6i and j in good yields (entries 9 and 10). The
dehydration was found to preferentially deliver the endocyclic internal more substituted double
bond over the exo-methylene bond. A direct method to synthesize such compounds would be
difficult.
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Table 2: One-pot access to β,-unsaturated and non-conjugated carbonyl compounds from
selected tertiaryhomoallyl alcoholsa
Entry Homoallylic
Product
Yield (%)
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alcohol
1
5a
5b
6a
6b
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4
5c
6c
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74
5d
6d
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5e
5f
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5g
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0.7:1
9
6i
6j
10
5j
aAll reactions were performed with 5 (0.5 mmol), PdCl2 (10 mol%), CrO3 (0.5 equiv), conc.
HCl (4.0 equiv), at 60 °C in CH3CN/H2O (7:1).
The reaction expectedly follows the hydroxyl-directed Wacker oxidation path, followed by
acid-assisted hydroxyl elimination. It is less likely that the double bond would first isomerize
to give allyl alcohol, followed by CrO3 effecting the oxidation similar to that of tertiary allyl
alcohols.28 The formation of compound 3 as major product when no acid is employed supports
the preceding claim. For compounds 6a-e, the formation of more substituted double bond in
conjugation with the aryl ring might prevent the isomerization to an α,β-unsaturated ketone
system. Similarly, for products 6f-j the endocyclic double bond is preferred over the exocyclic,
except for 6h'.
CONCLUSION
In conclusion, we have demonstrated a new method for the one-pot synthesis of β-substituted
and β,β-disubstituted α,β-unsaturated methyl ketones from homoallyl alcohols by sequential
PdCl2/CrO3 promoted Wacker process followed by acid-mediated dehydration reaction. We
also explored internal homoallyl alcohols which resulted in an excellent regioselective
formation of non-conjugated unsaturated carbonyl compounds under the optimized conditions.
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A new starting material based synthesis of α,β-unsaturated and non-conjugated ketones is
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demonstrated.
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EXPERIMENTAL SECTION
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1
General Information. H and 13C NMR spectra were recorded with a spectrometer operating
at 500 or 400 MHz and 125 or 100 MHz for proton and carbon nuclei, respectively. The
chemical shifts are based on TMS peak at  = 0.00 pm for proton NMR and CDCl3 peak at  =
77.00 ppm (t) in carbon NMR. IR spectra were obtained on an FT–IR spectrometer, and
samples were prepared by evaporation from CHCl3 on CsBr plates. High-resolution mass
spectra (HRMS) were obtained using positive electrospray ionization by TOF method.
General procedure for one-pot synthesis of unsaturated carbonyl compounds. To a stirred
solution of homoallyl alcohol (1, 3 or 5, 0.5 mmol) in CH3CN (3.5 mL) and H2O (0.5 mL) were
added PdCl2 (7.2 mg, 0.05 mmol, 10 mol%) and CrO3 (25.0 mg, 0.25 mmol, 0.5 equiv) at room
temperature. The reaction mixture was warmed to 60 ºC and stirred for 8-18 h. After
completion of reaction (monitored by TLC), conc. HCl (1.15 mL, 4.0 equiv) was added and
stirred for another 1 h at same temperature. The reaction mixture was then filtered through a
small pad of silica gel and washed with EtOAc and the filtrate concentrated. The residue was
purified by silica gel column chromatography using petroleum ether/EtOAc (85-95:15-5) as an
eluent to afford the unsaturated carbonyl compounds 2a-r, 4a-g, 6a-j respectively.
(E)-4-Phenyl-3-buten-2-one (2a):15e,29a yield 54.8 mg (75%); colorless oil; IR (CHCl3): max
=
3054, 3027, 2922, 1669, 1610, 1576, 1495, 1450, 1359, 1339, 1294, 1204, 1183, 1100, 1074,
977, 908, 691 cm-1; H NMR (400 MHz, CDCl3/TMS): δ = 7.56−7.54 (m, 2H), 7.51 (d, J =
1
16.1 Hz, 1H), 7.42−7.39 (m, 3H), 6.72 (d, J = 16.2 Hz, 1H), 2.39 (s, 3H); 13C{1H} NMR (100
MHz, CDCl3): δ = 198.4, 143.4, 134.3, 130.5, 128.9, 128.2, 127.1, 27.5; HRMS (ESI-TOF)
calcd for [C10H10O + H]+ 147.0804, found 147.0811.
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(E)-4-(3-Nitrophenyl)-3-buten-2-one (2b):29b yield 71.7 mg (75%); white solid, mp 98−99 oC;
IR (CHCl3): max = 3019, 1672, 1618, 1533, 1424, 1355, 1260, 1174, 1033, 975, 929, 770, 669
cm-1; 1H NMR (500 MHz, CDCl3/TMS) δ = 8.36 (d, J = 1.6 Hz, 1H), 8.21 (d, J = 0.6 Hz, 1H),
7.83 (d, J = 7.7 Hz, 1H), 7.57 (t, J = 8.0 Hz, 1H), 7.52 (d, J = 16.2 Hz, 1H), 6.81 (d, J = 16.2
Hz, 1H), 2.40 (s, 3H); 13C{1H} NMR (125 MHz, CDCl3) δ = 197.5, 148.6, 140.1, 136.2, 133.7,
130.0, 129.3, 124.6, 122.5, 27.9; HRMS (ESI-TOF) calcd for [C10H9NO3 + H]+ 192.0655,
found 192.0657.
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(E)-4-(4-Nitrophenyl)-3-buten-2-one (2c):29a yield 70.7 mg (74%); white solid, mp 116−118
oC; IR (CHCl3): max = 3020, 1695, 1674, 1615, 1597, 1523, 1434, 1347, 1257, 1174, 1111,
1020, 977, 929, 828, 669 cm-1; 1H NMR (400 MHz, CDCl3/TMS) δ = 8.26 (d, J = 8.8 Hz, 2H),
7.70 (d, J = 8.6 Hz, 2H), 7.54 (d, J = 16.3 Hz, 1H), 6.82 (d, J = 16.3 Hz, 1H), 2.43 (s, 3H);
13C{1H} NMR (125 MHz, CDCl3) δ = 197.6, 148.6, 140.6, 140.1, 130.3, 128.8, 124.2, 28.0;
HRMS (ESI-TOF) calcd for [C10H9NO3 + H]+ 192.0655, found 192.0657.
(E)-4-(3-Methoxyphenyl)-3-buten-2-one (2d):15e,29a yield 63.4 mg (72%); colorless oil; IR
(CHCl3): max = 3011, 2961, 2837, 1668, 1610, 1582, 1488, 1455, 1434, 1360, 1160, 1083,
1
1047, 1006, 978, 950, 933, 870, 836, 686, 667 cm-1; H NMR (400 MHz, CDCl3/TMS) δ =
7.48 (d, J = 16.2 Hz, 1H), 7.29 (t, J = 8.0 Hz, 1H), 7.11 (d, J = 7.5 Hz, 1H), 7.04 (s, 1H), 6.93
(dd, J = 8.2, 1.0 Hz, 1H), 6.68 (d, J = 16.2 Hz, 1H), 3.81 (s, 3H), 2.36 (s, 3H); 13C{1H} NMR
(100 MHz, CDCl3) δ = 198.3, 159.9, 143.3, 135.7, 129.9, 127.3, 120.9, 116.3, 113.0, 55.2,
27.4; HRMS (ESI-TOF) calcd for [C11H12O2 + Na]+ 199.0730, found 199.0737.
(E)-4-(4-Methoxyphenyl)-3-buten-2-one (2e):15e,29a yield 64.3 mg (73%); yellow solid, mp
69−71 oC; IR (CHCl3): max = 3014, 2959, 2938, 2846, 1683, 1664, 1625, 1602, 1573, 1511,
1464, 1423, 1360, 1331, 1301, 1173, 1109, 1022, 989, 854, 819, 667 cm-1; 1H NMR (500 MHz,
CDCl3/TMS) δ = 7.48 (d, J = 8.6 Hz, 2H), 7.46 (d, J = 15.8 Hz, 1H), 6.90 (d, J = 8.8 Hz, 2H),
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6.59 (d, J = 16.2 Hz, 1H), 3.83 (s, 3H), 2.35 (s, 3H); C{1H} NMR (125 MHz, CDCl3) δ =
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198.4, 161.6, 143.2, 129.9, 127.0, 125.0, 114.4, 55.3, 27.3; HRMS (ESI-TOF) calcd for
[C11H12O2 + Na]+ 199.0730, found 199.0723.
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(E)-4-p-Tolyl-3-buten-2-one (2f):15e,29a yield 61.7 mg (77%); colorless oil; IR (CHCl3): max
=
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3026, 2921, 1664, 1618, 1569, 1512, 1413, 1357, 1326, 1293, 1180, 1109, 983, 909, 861, 804,
765, 709, 602 cm-1; 1H NMR (500 MHz, CDCl3/TMS) δ = 7.46 (d, J = 16.3 Hz, 1H), 7.44 (d,
J = 8.0 Hz, 2H), 7.20 (d, J = 8.0 Hz, 2H), 6.68 (d, J = 16.3 Hz, 1H), 2.38 (s, 3H), 2.35 (s, 3H);
13C{1H} NMR (125 MHz, CDCl3) δ = 198.5, 143.5, 141.0, 131.6, 129.7, 128.2, 126.2, 27.4,
21.5; HRMS (ESI-TOF) calcd for [C11H12O + H]+ 161.0961, found 161.0964.
(E)-4-(2,3-Dimethoxyphenyl)-3-buten-2-one (2g):29b yield 73.2 mg (71%); colorless oil; IR
(CHCl3): max = 3013, 2937, 1690, 1671, 1644, 1607, 1579, 1479, 1428, 1361, 1223, 1172,
1090, 1072, 1005, 924, 782, 668 cm-1; 1H NMR (400 MHz, CDCl3/TMS) δ = 7.85 (d, J = 16.5
Hz, 1H), 7.16 (d, J = 7.9 Hz, 1H), 7.05 (t, J = 8.0 Hz, 1H), 6.94 (d, J = 8.0 Hz, 1H), 6.71 (d, J
= 16.5 Hz, 1H), 3.86 (s, 6H), 2.38 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ = 198.8, 153.0,
148.4, 138.0, 128.5, 128.4, 124.2, 118.8, 114.1, 61.3, 55.8, 27.2; HRMS (ESI-TOF) calcd for
[C12H14O3 + Na]+ 229.0835, found 229.0835.
(E)-4-(3,4-Dimethoxyphenyl)-3-buten-2-one (2h):29c yield 75.3 mg (73%); yellow solid, mp
65−66 oC; IR (CHCl3): max = 3019, 2963, 2937, 2840, 1683, 1666, 1639, 1622, 1597, 1582,
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1515, 1465, 1441, 1421, 1360, 1338, 1307, 1296, 1160, 1140, 1024, 974, 803, 666 cm-1; H
NMR (400 MHz, CDCl3/TMS) δ = 7.43 (d, J = 16.2 Hz, 1H), 7.10 (d, J = 8.3 Hz, 1H), 7.04 (s,
1H), 6.84 (d, J = 8.3 Hz, 1H), 6.57 (d, J = 16.2 Hz, 1H), 3.89 (s, 3H), 3.88 (s, 3H), 2.34 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3) δ = 198.4, 151.2, 149.2, 143.5, 127.3, 125.2, 123.0, 111.0,
109.5, 55.9, 55.8, 27.3; HRMS (ESI-TOF) calcd for [C12H14O3 + Na]+ 229.0835, found
229.0838.
(E)-4-(2,5-Dimethoxyphenyl)-3-buten-2-one (2i):30a yield 76.3 mg (74%); white solid, mp
49−51 oC; IR (CHCl3): max = 3004, 2945, 2836, 1667, 1645, 1620, 1603, 1578, 1497, 1465,
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1428, 1360, 1321, 1287, 1254, 1179, 1047, 1024, 982, 841, 807, 717 cm-1; 1H NMR (400 MHz,
CDCl3/TMS) δ = 7.86 (d, J = 16.5 Hz, 1H), 7.07 (d, J = 3.0 Hz, 1H), 6.93 (dd, J = 9.0, 3.0 Hz,
1H), 6.86 (d, J = 9.0 Hz, 1H), 6.71 (d, J = 16.5 Hz, 1H), 3.85 (s, 3H), 3.79 (s, 3H), 2.39 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3) δ = 199.1, 153.6, 152.8, 138.5, 127.9, 123.9, 117.6, 112.6,
112.5, 56.1, 55.8, 27.1; HRMS (ESI-TOF) calcd for [C12H14O3 + Na]+ 229.0835, found
229.0835.
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(E)-4-(2,3-Dimethoxynaphthalen-1-yl)-3-buten-2-one (2j): yield 96.1 mg (75%); yellow oil; IR
(CHCl3): max = 3018, 2929, 2847, 1666, 1601, 1465, 1422, 1361, 1339, 1177, 1153, 1119,
1042, 1020, 927, 835, 668 cm-1; 1H NMR (400 MHz, CDCl3/TMS) δ = 8.07 (d, J = 16.6 Hz,
1H), 8.02 (dd, J = 7.6, 2.5 Hz, 1H), 7.73 (dd, J = 8.2, 1.7 Hz, 1H), 7.45−7.38 (m, 2H), 7.21 (s,
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1H), 6.94 (d, J = 16.6 Hz, 1H), 4.00 (s, 3H), 3.88 (s, 3H), 2.47 (s, 3H); C{1H} NMR (100
MHz, CDCl3) δ = 198.9, 151.7, 148.6, 136.8, 133.7, 131.4, 127.2, 127.1, 125.7, 124.8, 124.2,
123.9, 109.0, 60.9, 55.7, 27.8; HRMS (ESI-TOF) calcd for [C16H16O3 + Na]+ 279.0992, found
279.0991.
(E)-4-Mesityl-3-buten-2-one (2k):30a yield 72.5 mg (77%); colorless oil; IR (CHCl3): max
=
3012, 2962, 2862, 1670, 1609, 1567, 1458, 1359, 1304, 1254, 1174, 1150, 1031, 985, 898, 857,
721, 667 cm-1; 1H NMR (400 MHz, CDCl3/TMS) δ = 7.68 (d, J = 16.6 Hz, 1H), 6.90 (s, 2H),
6.34 (d, J = 16.6 Hz, 1H), 2.39 (s, 3H), 2.33 (s, 6H), 2.29 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3) δ = 198.5, 142.0, 138.5, 136.7, 132.3, 130.8, 129.2, 27.4, 21.04, 21.0; HRMS (ESI-
TOF) calcd for [C13H16O + H]+ 189.1274, found 189.1274.
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(E)-4-(Piperonyl)-3-buten-2-one (2l):30b yield 71.3 mg (75%); white solid, mp 65−66 C; IR
(CHCl3): max = 3019, 2897, 1666, 1625, 1601, 1505, 1491, 1449, 1359, 1257, 1179, 1104,
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1041, 973, 932, 865, 669 cm-1; H NMR (500 MHz, CDCl3/TMS) δ = 7.42 (d, J = 16.1 Hz,
1H), 7.04 (s, 1H), 7.02 (d, J = 8.0 Hz, 1H), 6.82 (d, J = 8.0 Hz, 1H), 6.55 (d, J = 16.1 Hz, 1H),
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6.01 (s, 2H), 2.35 (s, 3H); C{1H} NMR (125 MHz, CDCl3) δ = 198.3, 149.8, 148.4, 143.2,
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128.8, 125.3, 124.8, 108.6, 106.5, 101.6, 27.5; HRMS (ESI-TOF) calcd for [C11H10O3 + Na]+
213.0522, found 213.0524.
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(E)-4-(4-Chlorophenyl)-3-buten-2-one (2m):17,29a yield 65.0 mg (72%); yellow solid, mp
47−48 oC; IR (CHCl3): max = 3016, 2921, 2850, 1686, 1660, 1610, 1590, 1491, 1406, 1361,
1317, 1092, 1013, 978, 866, 809, 688 cm-1; 1H NMR (400 MHz, CDCl3/TMS) δ = 7.46 (dd, J
= 8.7, 1.0 Hz, 2H), 7.45 (d, J = 16.2 Hz, 1H), 7.36 (dd, J = 8.7, 2.2 Hz, 2H), 6.67 (d, J = 16.2
Hz, 1H), 2.37 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ = 198.2, 141.9, 136.4, 132.9, 129.4,
129.2, 127.4, 27.6; HRMS (ESI-TOF) calcd for [C10H9OCl + H]+ 181.0415, found 181.0413.
(E)-4-(2-Chlorophenyl)but-3-en-2-one (2n):30c yield 61.4 mg (68%); colorless oil; IR (CHCl3):
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max = 3063, 2924, 1693, 1672, 1618, 1610, 1591, 1471, 1442, 1360, 1315, 1285, 1258, 1178,
1126, 1100, 1052, 1038, 975, 910, 695 cm-1; 1H NMR (500 MHz, CDCl3/TMS) δ = 7.92 (d, J
= 16.3 Hz, 1H), 7.62 (d, J = 7.4 Hz, 1H), 7.41 (d, J = 7.8 Hz, 1H), 7.33−7.26 (m, 2H), 6.66 (d,
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J = 16.3 Hz, 1H), 2.41 (s, 3H); C{1H} NMR (125 MHz, CDCl3) δ = 198.3, 139.2, 135.1,
132.6, 131.2, 130.1, 129.6, 127.5, 127.2, 27.2; HRMS (ESI-TOF) calcd for [C10H9OCl + H]+
181.0415, found 181.0416.
(E)-4-(4-Fluorophenyl)-3-buten-2-one (2o):15e,29a yield 60.7 mg (74%); colorless oil; IR
(CHCl3): max = 3072, 3050, 2921, 2857, 1668, 1624, 1599, 1509, 1415, 1360, 1325, 1297,
1233, 1178, 1160, 1098, 978, 858, 819, 779, 733 cm-1; 1H NMR (400 MHz, CDCl3/TMS) δ =
7.55−7.52 (m, 2H), 7.47 (d, J = 16.2 Hz, 1H), 7.08 (t, J = 8.6 Hz, 2H), 6.64 (d, J = 16.2 Hz,
1H), 2.37 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ = 198.1, 164.0 (d, 1JC-F = 250 Hz), 142.0,
2
130.6, 130.2, 126.8, 116.1 (d, JC-F = 22 Hz), 27.6; HRMS (ESI-TOF) calcd for [C10H9OF +
H]+ 165.0710, found 165.0712.
(E)-4-(4-Hydroxyphenyl)but-3-en-2-one (2p):31a yield 60.8 mg (75%); white solid, mp
111−112 oC; IR (CHCl3): max = 3325, 3019, 1664, 1636, 1602, 1513, 1439, 1362, 1331, 1170,
1105, 1045, 975, 928, 823, 669 cm-1; 1H NMR (400 MHz, CDCl3/TMS) δ = 7.51 (d, J = 16.2
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Hz, 1H), 7.44 (d, J = 8.4 Hz, 2H), 6.91 (d, J = 8.4 Hz, 2H), 6.61 (d, J = 16.2 Hz, 1H), 2.39 (s,
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3H); C{1H} NMR (100 MHz, CDCl3) δ = 200.1, 159.0, 144.8, 130.4, 126.4, 124.3, 116.2,
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27.2; HRMS (ESI-TOF) calcd for [C10H10O2 + Na]+ 185.0573, found 185.0570.
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(E)-4-(2-Hydroxy-3-methoxyphenyl)-3-buten-2-one (2q):31b yield 68.2 mg (71%); colorless oil;
IR (CHCl3): max = 3398, 3014, 2940, 2842, 1666, 1639, 1620, 1604, 1588, 1481, 1442, 1362,
1257, 1185, 1072, 982, 922, 833, 667 cm-1; 1H NMR (500 MHz, CDCl3/TMS) δ = 7.84 (d, J =
16.5 Hz, 1H), 7.11 (dd, J = 7.4, 2.0 Hz, 1H), 6.89−6.83 (m, 2H), 6.80 (d, J = 16.5 Hz, 1H),
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6.23 (s, OH), 3.91 (s, 3H), 2.39 (s, 3H); C{1H} NMR (125 MHz, CDCl3) δ = 199.2, 146.8,
145.3, 138.2, 128.1, 120.8, 120.2, 119.8, 112.0, 56.2, 27.1; HRMS (ESI-TOF) calcd for
[C11H12O3 + Na]+ 215.0679, found 215.0679.
(E)-4-(4-Hydroxy-3-methoxyphenyl)-3-buten-2-one (2r):31b yield 72.1 mg (75%); white solid,
o
mp 87−88 C; IR (CHCl3): max = 3531, 3019, 2972, 2847, 1664, 1635, 1603, 1591, 1513,
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1465, 1430, 1361, 1257, 1184, 1123, 1034, 973, 929, 812, 669 cm-1; H NMR (400 MHz,
CDCl3/TMS) δ = 7.43 (d, J = 16.2 Hz, 1H), 7.10−7.03 (m, 2H), 6.91 (d, J = 8.1 Hz, 1H), 6.57
(d, J = 16.2 Hz, 1H), 6.27 (brs, 1H, OH), 3.90 (s, 3H), 2.35 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3) δ = 198.6, 148.3, 146.9, 143.9, 126.8, 124.8, 123.4, 114.9, 109.4, 55.9, 27.2; HRMS
(ESI-TOF) calcd for [C11H12O3 + Na]+ 215.0679, found 215.0679.
(E)-4-Phenyl-3-penten-2-one (4a):32a yield 60.1 mg (75%); colorless oil; IR (CHCl3): max
=
3018, 2925, 2855, 1678, 1600, 1576, 1446, 1376, 1357, 1271, 1184, 1028, 963, 928, 854, 771,
696, 668 cm-1; 1H NMR (400 MHz, CDCl3/TMS) δ = 7.48−7.47 (m, 2H), 7.39−7.37 (m, 3H),
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6.51 (s, 1H), 2.54 (s, 3H), 2.29 (s, 3H); C{1H} NMR (100 MHz, CDCl3) δ = 198.9, 153.9,
142.5, 129.1, 128.5, 126.5, 124.5, 32.2, 18.3; HRMS (ESI-TOF) calcd for [C11H12O + Na]+
183.0780, found 183.0785.
(E)-4-(Biphenyl-4-yl)-3-penten-2-one (4b): yield 70.9 mg (60%); white solid, mp 120−121 oC;
IR (CHCl3): max = 3019, 1677, 1597, 1554, 1488, 1426, 1354, 1047, 1029, 963, 929, 832, 669
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cm-1; H NMR (500 MHz, CDCl3/TMS) δ = 7.65−7.59 (m, 6H), 7.48 (t, J = 7.8 Hz, 2H),
7.41−7.38 (m, 1H), 6.61 (s, 1H), 2.60 (s, 3H), 2.34 (s, 3H); 13C{1H} NMR (125 MHz, CDCl3)
δ = 198.9, 153.3, 142.0, 141.2, 140.2, 128.7, 127.7, 127.2, 127.0, 126.9, 124.3, 32.3, 18.2;
HRMS (ESI-TOF) calcd for [C17H16O + Na]+ 259.1093, found 259.1091.
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(E)-4-(4-Methoxyphenyl)-3-penten-2-one (4c):32b yield 55.2 mg (58%); white solid, mp 67−68
oC; IR (CHCl3): max = 3017, 2960, 2936, 2839, 1674, 1592, 1570, 1512, 1463, 1440, 1419,
1377, 1358, 1291, 1179, 1033, 963, 827, 667 cm-1; 1H NMR (400 MHz, CDCl3/TMS) δ = 7.47
(d, J = 8.8 Hz, 2H), 6.90 (d, J = 8.8 Hz, 2H), 6.50 (s, 1H), 3.83 (s, 3H), 2.52 (s, 3H), 2.28 (s,
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3H); C{1H} NMR (100 MHz, CDCl3) δ = 198.8, 160.5, 153.4, 134.5, 127.9, 122.9, 113.9,
55.3, 32.3, 18.0; HRMS (ESI-TOF) calcd for [C12H14O2 + Na]+ 213.0886, found 213.0889.
(E)-4-(Naphthalen-2-yl)-3-penten-2-one (4d): yield 61.0 mg (58%); yellow oil; IR (CHCl3):
max = 3058, 3006, 2925, 2850, 1680, 1627, 1597, 1503, 1468, 1434, 1361, 1281, 1229, 1193,
1129, 1018, 962, 896, 861, 819, 667 cm-1; 1H NMR (400 MHz, CDCl3/TMS) δ = 9.67 (s, 1H),
7.89−7.83 (m, 3H), 7.61 (dd, J = 8.6, 2.0 Hz, 1H), 7.54−7.49 (m, 2H), 6.67 (d, J = 1.1 Hz, 1H),
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2.66 (d, J = 1.2 Hz, 3H), 2.34 (s, 3H); C{1H} NMR (125 MHz, CDCl3) δ = 198.9, 153.6,
139.6, 133.5, 133.1, 128.5, 128.2, 127.6, 126.7, 126.5, 126.2, 124.8, 124.0, 32.3, 18.3; HRMS
(ESI-TOF) calcd for [C15H14O + Na]+ 233.0937, found 233.0931.
(E)-4-Phenyl-3-hexen-2-one (4e):33a yield 47.9 mg (55%); colorless oil; IR (CHCl3): max
=
2969, 2933, 1679, 1597, 1572, 1357, 1180, 1099, 1020, 916, 736, 696, 650 cm-1; 1H NMR (400
MHz, CDCl3/TMS) δ = 7.45−7.43 (m, 2H), 7.39−7.37 (m, 3H), 6.40 (s, 1H), 3.05 (q, J = 7.5
Hz, 2H), 2.28 (s, 3H), 1.05 (t, J = 7.5 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ = 198.5,
160.4, 141.3, 132.3, 128.9, 128.5, 126.8, 124.2, 32.3, 24.4, 13.5; HRMS (ESI-TOF) calcd for
[C12H14O + Na]+ 197.0937, found 197.0933.
4,4-Diphenyl-3-buten-2-one (4f):33b yield 46.7 mg (42%); yellow oil; IR (CHCl3): max = 3057,
3027, 2928, 1684, 1664, 1591, 1569, 1491, 1445, 1354, 1178, 1075, 1022, 858, 699, 666 cm-1;
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1H NMR (500 MHz, CDCl3/TMS) δ = 7.51−7.49 (m, 3H), 7.45−7.32 (m, 5H), 7.28−7.24 (m,
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2H), 6.61 (s, 1H), 1.91 (s, 3H); C{1H} NMR (125 MHz, CDCl3) δ = 200.2, 153.9, 140.7,
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138.9, 129.5, 129.4, 128.7, 128.35, 128.3, 127.6, 30.3; HRMS (ESI-TOF) calcd for [C16H14O
+ Na]+ 245.0937, found 245.0935.
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1-(9H-Fluoren-9-ylidene)propan-2-one (4g):34a yield 68.3 mg (62%); yellow solid, mp 97−98
oC; IR (CHCl3): max = 3065, 2955, 2925, 2853, 1682, 1617, 1590, 1476, 1450, 1354, 1299,
1177, 1163, 1020, 980, 941, 846, 784, 728 cm-1; 1H NMR (500 MHz, CDCl3/TMS) δ = 8.79
(d, J = 7.8 Hz, 1H), 7.70 (d, J = 7.7 Hz, 1H), 7.64 (dd, J = 7.5, 2.1 Hz, 2H), 7.43 (dq, J = 7.5,
1.0 Hz, 1H), 7.33−7.27 (m, 3H), 7.09 (s, 1H), 2.52 (s, 3H); 13C{1H} NMR (125 MHz, CDCl3)
δ = 198.6, 145.9, 142.4, 141.3, 138.9, 135.3, 131.2, 130.7, 128.5, 128.2, 127.4, 121.1, 120.8,
119.9, 119.6, 32.4; HRMS (ESI-TOF) calcd for [C16H12O + Na]+ 243.0780, found 243.0782.
(E)-2-Phenyl-2-undecen-5-one (6a): yield 77.0 mg (63%); yellow oil; IR (CHCl3): max = 3063,
3020, 3000, 2957, 2931, 2858, 1754, 1625, 1601, 1495, 1448, 1407, 1376, 1261, 1178, 1102,
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1072, 1028, 961, 920, 876, 821, 700, 667 cm-1; H NMR (500 MHz, CDCl3/TMS) δ = 7.99 (d,
J = 7.3 Hz, 2H), 7.51−7.27 (m, 3H), 5.95 (td, J = 7.2, 1.1 Hz, 1H), 3.34 (d, J = 7.2 Hz, 2H),
2.50 (t, J = 7.5 Hz, 2H), 2.08 (s, 3H), 1.59−1.45 (m, 2H), 1.34−1.28 (m, 6H), 0.92 (t, J = 7.5
13
Hz, 3H); C {1H} NMR (125 MHz, CDCl3) δ = 209.0, 143.2, 138.2, 128.2, 127.1, 125.8,
119.5, 43.2, 42.6, 31.6, 28.9, 23.8, 22.5, 16.3, 14.0; HRMS (ESI-TOF) calcd for [C17H24O +
H]+ 245.1900, found 245.1894.
1-(9H-Fluoren-9-ylidene)nonan-3-one (6b): yield 118.7 mg (78%); yellow oil; IR (CHCl3):
max = 2955, 2930, 2856, 1714, 1608, 1512, 1464, 1414, 1376, 1290, 1248, 1180, 1035, 911,
830, 734 cm-1; 1H NMR (400 MHz, CDCl3/TMS) δ = 7.78−7.68 (m, 4H), 7.41−7.28 (m, 4H),
7.03 (t, J = 7.0 Hz, 1H), 3.93 (d, J = 7.0 Hz, 2H), 2.59 (t, J = 7.3 Hz, 2H), 1.69−1.62 (m, 2H),
1.33−126 (m, 6H), 0.94−0.87 (m, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 207.3, 141.2, 139.0,
138.8, 137.3, 137.0, 128.3, 127.9, 127.1, 127.0, 124.6, 120.23, 120.16, 120.0, 119.5, 43.0, 42.6,
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31.6, 28.8, 23.8, 22.5, 14.0; HRMS (ESI-TOF) calcd for [C22H24O + Na]+ 327.1719, found
327.1722.
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(E)-2-(4-Methoxyphenyl)-2-undecen-5-one (6c): yield 94.7 mg (69%); colorless oil; IR
(CHCl3): max = 2956, 2931, 2857, 1709, 1669, 1609, 1512, 1464, 1376, 1290, 1247, 1179,
1034, 909, 830, 733 cm-1; 1H NMR (400 MHz, CDCl3/TMS) δ = 7.34 (d, J = 8.9 Hz, 2H), 6.86
(d, J = 8.9 Hz, 2H), 5.87 (td, J = 6.0, 1.2 Hz, 1H), 3.80 (s, 3H), 3.30 (d, J = 7.2 Hz, 2H), 2.47
(t, J = 7.5 Hz, 2H), 2.02 (s, 3H), 1.30−1.25 (m, 8H), 0.88−0.86 (m, 3H); 13C{1H} NMR (100
MHz, CDCl3) δ = 209.2, 158.8, 137.5, 135.7, 126.8, 117.8, 113.6, 55.3, 43.2, 42.5, 31.6, 28.9,
23.8, 22, 5, 16.3, 14.0; HRMS (ESI-TOF) calcd for [C18H26O2 + Na]+ 297.1825, found
297.1816.
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(E)-4-(4-Methoxyphenyl)-1-phenyl-3-penten-1-one (6d): yield 98.5 mg (74%); colorless oil; IR
(CHCl3): max = 3155, 2959, 2930, 2840, 1682, 1607, 1512, 1465, 1449, 1380, 1324, 1290,
1247, 1180, 1096, 1034, 898, 832, 676 cm-1; 1H NMR (400 MHz, CDCl3/TMS) δ = 8.01 (dd,
J = 7.7, 1.5 Hz, 2H), 7.60−7.41 (m, 3H), 7.36 (d, J = 8.8 Hz, 2H), 6.85 (d, J = 8.8 Hz, 2H),
6.03 (tq, J = 6.9, 1.3 Hz, 1H), 3.90 (dd, J = 6.9, 0.8 Hz, 2H), 3.81 (s, 3H), 2.15 (s, 3H); 13C{1H}
NMR (125 MHz, CDCl3) δ = 198.0, 158.8, 137.4, 136.8, 135.7, 133.1, 128.3, 126.8, 118.1,
113.5, 55.3, 39.0, 16.4; HRMS (ESI-TOF) calcd for [C18H18O2 + Na]+ 289.1199, found
289.1193.
(E)-1,4-Diphenyl-3-penten-1-one (6e):34b yield 80.3 mg (68%); colorless oil; IR (CHCl3): max
= 3085, 3058, 3034, 2872, 2924, 2861, 1684, 1617, 1598, 1581, 1493, 1447, 1380, 1323, 1180,
1158, 1072, 1001, 910, 736, 697 cm-1; 1H NMR (500 MHz, CDCl3/TMS) δ = 8.02 (dd, J = 8.3,
1.7 Hz, 2H), 7.60−7.57 (m, 1H), 7.50−7.47 (m, 2H), 7.42 (dd, J = 7.8, 1.0 Hz, 2H), 7.32 (t, J =
7.5 Hz, 2H), 7.25−7.23 (m, 1H), 6.12 (td, J = 6.8, 1.3 Hz, 1H), 3.91 (d, J = 6.8 Hz, 2H), 2.13
(d, J = 1.0 Hz, 3H); 13C{1H} NMR (125 MHz, CDCl3) δ = 197.9, 143.2, 138.1, 136.8, 133.1,
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128.6, 128.3, 128.2, 127.0, 125.8, 119.7, 39.0, 16.5; HRMS (ESI-TOF) calcd for [C17H16O +
Na]+ 259.1093, found 259.1092.
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1-(5-Methoxy-3,4-dihydronaphthalen-1-yl)propan-2-one (6f): yield 73.5 mg (68%); yellow
oil; IR (CHCl3): max = 3016, 2937, 2837, 1709, 1573, 1473, 1461, 1439, 1408, 1356, 1347,
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1299, 1262, 1193, 1161, 1140, 1050, 931, 910, 853, 825, 667 cm-1; H NMR (400 MHz,
CDCl3/TMS) δ = 7.13 (t, J = 8.0 Hz, 1H), 6.78 (d, J = 8.0 Hz, 1H), 6.74 (d, J = 8.0 Hz, 1H);
6.01 (t, J = 4.5 Hz, 1H), 3.83 (s, 3H), 3.46 (s, 2H), 2.80 (t, J = 8.2 Hz, 2H), 2.36−2.28 (m, 2H),
2.12 (s, 3H); C{1H}NMR (100 MHz, CDCl3) δ = 208.2, 156.1, 135.1, 130.9, 129.9, 126.6,
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124.1, 115.8, 110.0, 55.5, 49.6, 28.5, 22.7, 19.7; HRMS (ESI-TOF) calcd for [C14H16O2 + Na]+
239.1043, found 239.1045.
1-(3,4-Dihydronaphthalen-1-yl)propan-2-one (6g): yield 52.1 mg (56%); yellow oil; IR
(CHCl3): max = 3059, 3020, 2934, 2885, 2831, 1710, 1675, 1579, 1488, 1449, 1427, 1355,
1325, 1225, 1159, 1039, 1022, 912, 790, 735 cm-1; H NMR (500 MHz, CDCl3/TMS) δ =
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7.19−7.08 (m, 4H), 6.01 (t, J = 4.5 Hz, 1H), 3.48 (s, 2H), 2.81 (t, J = 8.0 Hz, 2H), 2.37−2.32
(m, 2H), 2.15 (s, 3H); 13C{1H} NMR (125 MHz, CDCl3) δ = 207.9, 136.2, 134.1, 130.9, 129.6,
127.7, 127.2, 126.5, 122.8, 49.1, 28.5, 28.0, 23.2; HRMS (ESI-TOF) calcd for [C13H14O +
Na]+ 209.0937, found 209.0935.
1-(1H-Inden-3-yl)propan-2-one (6h)35a and (E)-1-(2,3-dihydro-1H-inden-1-ylidene)propan-2-
one (6h'):35b mixture (0.7:1), yield 48.2 mg (56%); colorless oil; IR (CHCl3): max = 3068,
3041, 3019, 2922, 2855, 1712, 1676, 1646, 1594, 1473, 1461, 1438, 1394, 1361, 1322, 1278,
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1256, 1223, 1188, 1170, 1106, 1039, 1017, 982, 962, 845 cm-1; H NMR (400 MHz,
CDCl3/TMS) of the mixture δ = 7.64 (d, J = 7.7 Hz, 1H), 7.48 (d, J = 2.6 Hz, 1H), 7.47 (d, J =
1.6 Hz, 2H), 7.40−7.21 (m, 4H), 6.75 (t, J = 2.5 Hz, 1H), 6.41 (t, J = 1.0 Hz, 1H), 3.66 (d, J =
1.2 Hz, 2H), 3.41 (d, J = 1.2 Hz, 2H), 3.32−3.28 (m, 2H), 3.08−3.06 (m, 2H), 2.32 (s, 3H), 2.20
(s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ = 206.2, 198.2, 161.9, 150.2, 144.0, 139.9, 137.2,
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132.1, 131.1, 126.7, 126.2, 125.7, 124.9, 123.8, 121.5, 119.1, 115.1, 43.5, 38.0, 31.9, 31.6,
30.7, 29.1; HRMS (ESI-TOF) calcd for [C12H12O + H]+ 173.0961, found 173.0955.
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1-(3,4-Dihydronaphthalen-1-yl)nonan-3-one (6i): yield 96.0 mg (71%); yellow oil; IR
(CHCl3): max = 3057, 3018, 2931, 2858, 1713, 1487, 1450, 1412, 1370, 1278, 1234, 1160,
1127, 1081, 1038, 1022, 938, 868, 817, 790, 667 cm-1; 1H NMR (400 MHz, CDCl3/TMS) δ =
7.22−7.19 (m, 2H), 7.18−7.14 (m, 2H), 5.86 (t, J = 4.5 Hz, 1H), 2.75−2.70 (m, 4H), 2.65−2.61
(m, 2H), 2.39 (t, J = 7.5 Hz, 2H), 2.26−2.21 (m, 2H), 1.64−1.51 (m, 2H), 1.34−1.19 (m, 6H),
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0.88 (t, J = 6.8 Hz, 3H); C{1H} NMR (100 MHz, CDCl3) δ = 210.9, 136.7, 135.3, 134.3,
127.7, 126.7, 126.4, 125.3, 122.4, 43.1, 41.6, 31.6, 28.9, 28.3, 26.6, 23.8, 23.0, 22.5, 14.0;
HRMS (ESI-TOF) calcd for [C19H26O + Na]+ 293.1876, found 293.1867.
3-(3,4-Dihydronaphthalen-1-yl)-1-phenylpropan-1-one (6j): yield 99.7 mg (76%); yellow oil;
IR (CHCl3): max = 3061, 3033, 2931, 2888, 2833, 1685, 1488, 1448, 1359, 1291, 1236, 1204,
1
1178, 975, 911, 765, 690 cm-1; H NMR (400 MHz, CDCl3/TMS) δ = 7.97 (dd, J = 8.2, 2.2
Hz, 2H), 7.56 (t, J = 7.4 Hz, 1H), 7.49−7.45 (m, 2H), 7.31−7.16 (m, 4H), 5.96 (t, J = 4.5 Hz,
1H), 3.23 (t, J = 7.7 Hz, 2H), 2.93 (t, J = 7.5 Hz, 2H), 2.75 (t, J = 8.0 Hz, 2H), 2.29−2.25 (m,
2H); 13C{1H} NMR (100 MHz, CDCl3) δ 199.8, 136.9, 136.8, 135.4, 134.3, 132.9, 128.5,
128.0, 127.7, 126.7, 126.4, 125.5, 122.4, 37.7, 28.2, 27.1, 23.0; HRMS (ESI-TOF) calcd for
[C19H18O + Na]+ 285.1250, found 285.1238.
ASSOCIATED CONTENT
Acknowledgements
This activity was supported by the Council of Scientific and Industrial Research (CSIR) New
Delhi [Grant No. 02 (0158)/13/EMR-II], India. Financial support received from CSIR-India
(fellowship to V.B.) is gratefully acknowledged.
Supporting Information
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Copies of 1H and 13C NMR spectra for all compounds. This material is available free of charge
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via the Internet at http://pubs.acs.org.
Author Information
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Corresponding Author
*Email: rfernand@chem.iitb.ac.in
Notes
The authors declare no competing financial interest.
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