Harnessing Nucleophilicity of Allenol Ester with p-Quinone Methides via Gold Catalysis: Application to the Synthesis of Diarylmethine-Substituted Enones

Article abstract of DOI:10.1021/acs.joc.8b01294

A gold(I)-catalyzed protocol for intermolecular 1,6-conjugate addition of nucleophilic allenol ester generated in situ through [3,3]-sigmatropic rearrangement with p-quinone methides (p-QMs) has been developed. The gold catalyst plays a dual role by the acid-triggered activation of alkynes and at the same time as a Lewis acid for activation of p-QMs toward nucleophilic attack. This method enables rapid access to a wide range of densely functionalized diarylmethine-substituted enones, a Morita-Baylis-Hillman (MBH) product with high selectivity, excellent yields, and broad substrate scope.

Full text of DOI:10.1021/acs.joc.8b01294

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Article
Harnessing Nucleophilicity of Allenol Ester with p-Quinone Methides via Gold
Catalysis: Application to the Synthesis of Diarylmethine-Substituted Enones
Brijesh Sharma, Jayant Rathod, Rajesh G. Gonnade, and Pradeep Kumar
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b01294 • Publication Date (Web): 20 Jun 2018
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Harnessing Nucleophilicity of Allenol Ester with p-Quinone Methides via Gold
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Catalysis: Application to the Synthesis of Diarylmethine-Substituted Enones
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§
Brijesh M. Sharma,†, ‡Jayant Rathod, †, ‡ Rajesh G. Gonnade, ‡, and Pradeep Kumar†, ‡ *
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†Division of Organic Chemistry, CSIRꢀNational Chemical Laboratory, Puneꢀ411008, India.
‡Academy of Scientific and Innovative Research (AcSIR), New Delhi – 110025, India.
§ Physical and Materials Chemistry Division, CSIR – National Chemical Laboratory, Pune, India
.
*Corresponding Author. Fax: +91 020ꢀ25902629; Tel: +91 2025902050
E-mail: pk.tripathi@ncl.res.in
Table of Contents (TOC) Graphic
ABSTRACT
A gold (I) catalyzed protocol for intermolecular 1,6ꢀconjugate addition of nucleophilic allenol
ester generated in situ through [3,3]ꢀsigmatropic rearrangement with pꢀquinone methides
(pꢀQMs) has been developed. The gold catalyst plays a dual role by the πꢀacidꢀtriggered
activation of alkynes; and at the same time as a Lewis acid for activation of pꢀQMs towards
nucleophilic attack. This method enables rapid access to wide range of densely functionalized
diarylmethineꢀsubstituted enones, a MoritaꢀBaylisꢀHillman (MBH) product with high selectivity,
excellent yields, and broad substrate scope.
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INTRODUCTION
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In recent years, there has been tremendous upsurge of interest in the homogeneous gold
catalyzed activation of C−C triple bond and allenes for constructing novel molecular
architectures or structural core of natural products/analogs in a cascade fashion.1 The gold
catalyzed [3,3]ꢀsigmatropic rearrangement of propargylic acetate to allenol ester followed by
electrophilic activation by gold (I)/(III) complexes towards nucleophilic attack, encompassing
both interꢀ2 and intramolecular3 variants, are among the most exploited reactions (Figure 1, Path
I). However, till date, there are only few reports which deal with inherent nucleophilicity of in
situ generated allenol ester4 towards intermolecular electrophilic addition through gold catalyzed
[3,3]ꢀsigmatropic rearrangement reaction in C−C bond formation (Figure 1, Path II). In this
direction, recently Zhang and coꢀworkers first reported an intermolecular addition of the
nucleophilic allenol ester with electrophilic Nꢀiodosuccinimide (NIS) for the synthesis of αꢀ
iodoenones.5 Later, Hashmi and coꢀworkers exquisitely demonstrated the gold catalyzed
intermolecular trapping of the allenol ester with electrophilic oxocarbenium ions generated from
acetal derivatives for C(sp3)−C(sp2) bond formation.6 In this line, Bandini and coꢀworkers further
reported the goldꢀcatalyzed αꢀalkylation of allylic alcohols by trapping allenol ester as shown in
Figure 1.7
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In recent years, the pꢀQMs motifs have received considerable attention owing to their
Michael acceptor property towards various nucleophiles under Lewis or Brønsted acid catalysis.8,
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In 2016, Lin and coꢀworkers10 demonstrated the intermolecular 1,6ꢀconjugate arylation of pꢀ
QMs with electronꢀrich aromatic compounds for the synthesis of unsymmetrical triarylmethanes
under BF3·OEt2 catalysis.
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Figure1: Intermolecular nucleophilic trapping of allenol ester generated in situ via gold
catalyzed [3,3]ꢀsigmatropic rearrangement
Similarly Anand et al.11 and Li et al.12 reported 1,6ꢀconjugate allylation of pꢀQMs using B(C6F5)3
and Bi(OTf)3 respectively. Further Angle13 and China Raju14 exquisitely demonstrated Lewis
acid catalyzed intramolecular cyclization reaction on pꢀQMs utilizing terminators such as allyl
silanes and βꢀketo esters appended to pꢀQMs. Recently our group has also reported acid
catalyzed 1,6ꢀconjugate addition reaction of pꢀQMs with vinyl azides and butenolides.15 To the
best of our knowledge, the gold catalyzed activation of alkynes along with pꢀQMs towards 1,6ꢀ
conjugate addition has not yet been explored. In continuation with our ongoing research interest
for exploring the electrophilicity of pꢀQMs and its nucleophilic repertoire, we envisioned that
incipient allenol ester, generated from a propargylic acetate (pathꢀII) through a πꢀacidꢀtriggered
cascade, could serve as a nucleophilic source (Figure 1). Herein, we report the gold catalyzed
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intermolecular 1,6ꢀconjugate addition of nucleophilic allenol ester with pꢀQMs to furnish a
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variety of unsymmetrical diarylmethineꢀsubstituted enones.
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RESULTS AND DISCUSSION
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To test our hypothesis for gold catalyzed intermolecular nucleophilic addition, pꢀQMs 1a and the
propargylic ester 2a were selected as a model substrate. The various reaction conditions such as
catalyst, solvent, and temperature were screened and the results obtained are summarized in
Table 1.
Initially, no product formation was observed when the reaction was performed using
AuCl in toluene at 60 °C (Table 1, entry 1). Interestingly, when the solvent was changed from
toluene to CH2Cl2, the desired product 3a was obtained in moderate yield (56%) with exclusive
Zꢀselectivity (entry 2). When the reaction was performed at r.t for 24h, no improvement in the
yield was observed (entry 3). Further endeavours in optimizing the reaction condition using
AuCl3 in CH2Cl2, at r.t resulted only in 51% yield of 3a (entry 4).
Driven by the quest for optimisation of yields, we further explored various combinations
of Au(I)ꢀcomplexes and Ag(I) salts, accordingly, Ph3PAuCl/AgNTf2 in CH2Cl2 at r.t could not
lead to any improvement in the yield of the product (entry 5). Similarly, PPh3AuCl/AgNTf2 in
1
DCE at r.t resulted in formation of 3a with Z/E mixture (1.5:1) as confirmed by HꢀNMR
analysis (entry 6). Gratifyingly, when the reaction was performed using PPh3AuCl/AgNTf2 in
DCE at 80 °C, the yield was drastically increased to 95% with Zꢀselectivity and the reaction went
to completion within 1 min. As per above observations, when the reaction was performed at
higher temperature it furnished Zꢀselective product exclusively. Further screening of
SPhosAuCl/AgNTf2 catalyst gave almost comparable yield of 3a with Zꢀselectivity (entry 8).
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When dichloro(2ꢀpyridinecarboxylato)gold was used as a catalyst, the reaction became sluggish,
and resulted only in poor yield (24%) (entry 9).
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Furthermore, switching over from propargylic acetate to its pivaloyl ester, changed the
selectivity of the reaction significantly and the desired enone 3a was obtained in excellent yield
with Z/E ratio (4: 1) (entry 10). Moreover, use of different solvents such as toluene, MeCN and
1,4ꢀdioxane did not improve the yields further (entry 11ꢀ13). In order to study the role of silver
in the reaction some control experiments were performed. When the reaction was carried out
using only AgNTf2, the reaction became sluggish, took 3h for completion, and the desired
product was obtained in only 42% yield with complete Zꢀselectivity (entry 12). Also, to eliminate
the probable involvement of AgCl in reaction we first filtered off the precipitate from the
reaction mixture followed by addition of both the reactants 1 and 2 (entry 15). From the above
observations, we concluded that silver does not have a significant role in enhancing the rate of
reaction. But the Au(I)ꢀcomplex formed by exchange of counter ions from Ag(I) salts plays a
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dual role not only by
activating alkynes by Meyer–Schuster type [3,3]ꢀsigmatropic
rearrangement but also through Lewis acid mediated activation of pꢀQMs for 1,6ꢀconjugated
addition.
Having established the optimized conditions (Table 1, entry 7), we then set out to explore
the generality and the scope of gold catalyzed nucleophilic 1,6ꢀconjugate addition by reacting
broad range of pꢀQMs (1a−1j) and secondary propargylic acetates (2a−2f) having electronꢀ
neutral, ꢀreleasing, and ꢀwithdrawing groups (Scheme 1). The scope of the reaction was studied
by first varying pꢀQMs (1a−1j), with 1,3ꢀdiphenylꢀpropargylic acetate 2a which underwent
nucleophilic addition to deliver corresponding enones (3a−3j) in good to excellent yields
(71−96%) with exclusive Zꢀselectivity.
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Table 1: Optimization of reaction conditions a
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Yield %
Time
min
5
Entry
Catalyst
Solvent
Z: Eb
3a
1c
2 c
AuCl
AuCl
toluene
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
DCE
N.R
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ꢀꢀ
Z
Z
Z
Z
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3 d
AuCl
24h 48
4 d
AuCl3
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5
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50
5 c
Ph3PAuCl/AgNTf2
Ph3PAuCl/AgNTf2
Ph3PAuCl/AgNTf2
SPhosAuCl/AgNTf2
Dichloro(2ꢀpyridine carboxylato)Au
Ph3PAuCl/AgNTf2
Ph3PAuCl/AgNTf2
Ph3PAuCl/AgNTf2
Ph3PAuCl/AgNTf2
AgNTf2
6 d
60
1
59 1.5:1
7e
DCE
95
88
24
97
42
Z
Z
8 e
DCE
1
9 e
DCE
3h
1
Z
10e,f
11e
12e
13e
14
DCE
4:1
Z
toluene
CH3CN
1,4ꢀDioxane
DCE
1
3h N.R
ꢀꢀ
Z
1
24
42
74
3h
30
Z
15e,g
Ph3PAuNTf2
DCE
Z
[a]
Reaction conditions:, 0.1 mmol 1a, 1 equiv. 2a, 5 mol% catalyst, 5 mol % AgNTf2, unless otherwise
stated and 1 mL solvent, [b] Z:E selectivity determined using 1HꢀNMR, [c] Reaction carried out at 60 οC, [d]
Reaction carried out at r.t, [e] Reaction carried out at 80 °C, [f] Pivaloyl ester 2h was used, [g] Precipitate of
AgCl filtered off, [h] N.R. = No reaction.
Moreover, pꢀQMs derived from aromatic aldehydes having electronꢀdonating and electronꢀ
withdrawing substituents at C4, C3 and C5 were wellꢀtolerated under the reaction condition,
having minimal or no impact on the yields. The geometry of the enone double bond was
unambiguously determined by the single crystal Xꢀray analysis of 3i.
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Scheme 1: Substrate scope for the formation of internal enones
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Next, we examined the scope of propargylic acetate under the developed protocol.
Interestingly, various electronically different symmetrical and unsymmetrical secondary
propargylic acetates with linear and branched aliphatic substitution easily underwent 1,6ꢀ
conjugate addition with pꢀQMs to deliver the desired products (3k−3o) in good yields (73−89%).
Relatively less stable derivative of pꢀQMs 1k with 2,6ꢀdimethyl substituents also delivered the
desired addition product 3q in good yield.
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Scheme 2: Substrate scope for the formation of terminal enones
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Further, to demonstrate the versatility of this methodology, pꢀQMs were reacted with a
series of primary propargylic acetates (4a−4d) under the optimized reaction conditions so as to
get the enones with exoꢀdouble bond (Scheme 2). Gratifyingly 4a smoothly underwent
nucleophilic addition with pꢀQMs having alkyl, aryl, ꢀCO2Me, ꢀOMe, and chloro substitution at
the C4ꢀposition affording corresponding terminal enones (5a−5h) in moderate to good yields
(75−88%), irrespective of the electronic nature of the substituents.
Next, we studied an array of primary propargylic acetates (4a−4e) having different alkyl,
methoxy and bromo substitutions which readily underwent 1,6ꢀconjugate addition with pꢀQMs
resulting in the formation of product (5a−5k) in good to excellent yields (74−86%). The reaction
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with long chain aliphatic propargylic acetate 4e also led to the product formation 5l in 74%
yield. The structure of compound 5h and 5j was proven unambiguously by a singleꢀcrystal Xꢀray
analysis. It may be pertinent to mention here that structurally analogous products (diarylmethineꢀ
substituted enones) have been reported recently on the basis of asymmetric catalytic
intermolecular vinylogous RauhutꢀCurrier reaction of vinyl ketones with pꢀQMs.16
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Scheme 3: The plausible reaction mechanism
Mechanistically, the reaction proceeds by gold catalyzed activation of propargylic ester to
give intermediate A followed by [3,3]ꢀsigmatropic rearrangement generating nucleophilic allenol
ester B, which is further trapped by pꢀQMs C, activated by Auꢀcomplex to deliver the MBH
product D (Scheme 3). The selectivity can be rationalized on the basis of literature precedence by
Zhang et al. which demonstrates if reaction proceeds via formation of carboxyallene B (path a)
it leads to the formation of Zꢀselective product.5
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Scheme 4: Synthetic utility of enones
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To investigate the synthetic utility, the products 3d and 3f were subjected to DDQ
mediated cyclization to afford cyclic pꢀquinone 6a and 6b with extended conjugation (Scheme
4a), via oxidative dearomative pathway in excellent yields (82ꢀ86%). In yet another synthetic
transformation, 6b resulted in the formation of aromatized product with indene core 7b in
presence of BF3.OEt2 in moist CH2Cl2 at 0 °C. The structure of product 7b was unequivocally
determined by a single crystal Xꢀray analysis (Scheme 4b).The synthetic utility of this method
was further explored by carrying out deꢀtertꢀbutylation of 3a using anhydrous AlCl3 to deliver
product 8a in 75% yield, which represents the important structural motifs of various indene as
well as resveratrol derived natural products (Scheme 4c).
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CONCLUSIONS
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We have developed a gold (I) catalyzed [3,3]ꢀsigmatropic rearrangement of propargylic
acetate followed by trapping of incipient nucleophilic allenol ester with pꢀQMs. The developed
protocol demonstrates a wide substrate scope with an array of pꢀQMs and propargylic acetates
leading to the formation of MBH product, with excellent selectivity in favour of sole Zꢀisomer.
The product diarylmethineꢀsubstituted enones further served as an important building block to
synthesize highly functionalized indene derivatives via DDQ mediated oxidative dearomative
cyclization. Attempts to further explore the nucleophilicity of allenol ester with different
electrophilic motifs are currently under progress in our laboratory.
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EXPERIMENTAL SECTION
General Informations
Reactions were carried out under anhydrous conditions, using flameꢀdried glassware under a
positive pressure of argon, unless otherwise stated. 1, 2ꢀDichloroethane, CH2Cl2, Et3N, and
piperidine were distilled from CaH2. Et2O, toluene and THF were distilled from
Na/benzophenone. Other reagents were obtained from commercial suppliers and used as
received. Airꢀsensitive reagents and solutions were transferred by syringe or cannula and were
introduced into the apparatus through rubber septa. Reactions were monitored by thinꢀlayer
chromatography (TLC) with 0.25 mm preꢀcoated silicaꢀgel plates (60 F254). Plates were
visualized with either UV light, iodine adsorbed on silica gel, or by immersion in an ethanolic
solution of phosphomolybdic acid (PMA), pꢀanisaldehyde, or KMnO4, followed by heating with
1
a heat gun for ca. 15s. Flash chromatography was carried out on silica gel (230–400 mesh). H
and 13C NMR spectra were obtained with a 200, 400, or 500 MHz Bruker/JEOL spectrometer in
CDCl3. Coupling constants are given in Hertz. Chemical shifts are quoted in ppm relative to
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tetramethylsilane, using the residual solvent peak as a reference standard. The following
abbreviations are used to explain the multiplicities: s = singlet, d = doublet, t = triplet, q =
quartet, quint = quintet, m = multiplet and br = broad. HRMS (ESI+) spectra were recorded with
an ORBITRAP mass analyzer. Infrared (IR) spectra were recorded with a FTIR spectrometer as
thin films using NaCl plates, and wavenumbers are indicated in cm–1. Chemical nomenclature
was generated using ChemBioDraw Ultra 15.0. CCDC 1817114 (for 3i), CCDC 1817116 (for
5h), CCDC 1817117 (for 5j), and CCDC 1817115 (for 7b) contain the supplementary
crystallographic data for this paper. These data can be obtained free of charge from the
Cambridge Crystallographic Data Centre.
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I.
General Procedure for Synthesis of p-Quinone Methide (1):
In an oven dried DeanꢀStark apparatus, phenol (25.0 mmol) and the corresponding aldehyde
(25.0 mmol, 1 equiv.) were taken in toluene (100 mL), reaction mixture was heated to reflux
followed by drop wise addition of piperidine (50.0 mmol, 5 mL, 2 equiv.) within 1h. Then, the
reaction mixture was continued to reflux for 6 h. After cooling just below the boiling point of the
reaction mixture, acetic anhydride (50.0 mmol, 4.7 mL, 2 equiv.) was added and stirring was
continued for 30 min. Then the reaction mixture was poured on iceꢀwater (500 mL) with
continuous stirring and extracted with CH2Cl2 (4 × 200 mL). The combined organic phase was
dried over anhydrous Na2SO4 and the solvent was evaporated under reduced pressure. The crude
products were purified by column chromatography and further recrystallized from nꢀhexane,
affording pꢀquinone methide (1aꢀ1j) in good yields. Compound 1k was prepared according to
literature report.8a
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4-Benzylidene-2,6-di-tert-butylcyclohexa-2,5-dien-1-one (1a):8 After column purification
compound was obtained in 76% yield, (5.6 g). 1H NMR (200MHz, CDCl3) δ = 7.53 (d, J = 2.3 Hz, 1
H), 7.09 (s, 1 H), 7.03 ꢀ 6.95 (m, 3 H), 6.94 ꢀ 6.86 (m, 1 H), 6.05 (s, 2 H), 1.33 (d like, J = 2.5 Hz, 18 H).
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2,6-Di-tert-butyl-4-(4-methylbenzylidene)cyclohexa-2,5-dien-1-one (1b):8 After column
purification compound was obtained in 65% yield, (5.1 g). 1H NMR (200MHz, CDCl3) δ = 7.58
(d like, J = 1.9 Hz, 1 H), 7.45 ꢀ 7.36 (m, 2 H), 7.34 ꢀ 7.24 (m, 2 H), 7.20 (s, 1 H), 7.04 (d like, J =
2.3 Hz, 1 H), 2.44 (s, 3 H), 1.35 (d like, J = 5.2 Hz, 18 H).
2,6-Di-tert-butyl-4-(4-methoxybenzylidene)cyclohexa-2,5-dien-1-one (1c):8 After column
purification compound was obtained in 82% yield, (6.7 g). 1H NMR (200MHz, CDCl3) δ = 7.57
(d like, J = 2.1 Hz, 1 H), 7.46 (d, J = 8.7 Hz, 2 H), 7.15 (s, 1 H), 7.05 ꢀ 6.93 (m, 3 H), 3.88 (s, 3
H), 1.33 (d like, J = 3.0 Hz, 18 H).
2,6-Di-tert-butyl-4-(3,4-dimethoxybenzylidene)cyclohexa-2,5-dien-1-one (1d):8 After column
purification compound was obtained in 72% yield, (6.4 g). 1H NMR (400MHz, CDCl3) δ = 7.63
(s, 1 H), 7.16 (s, 1 H), 7.07 ꢀ 7.02 (m, 2 H), 6.96 (s, 2 H), 3.98 (s, 3 H), 3.95 (s, 3 H), 1.36 (d like,
J = 4.9 Hz, 18 H).
2,6-Di-tert-butyl-4-(3,4,5-trimethoxybenzylidene)cyclohexa-2,5-dien-1-one
(1e):8
After
column purification compound was obtained in 65% yield, (6.2 g).1H NMR (200MHz, CDCl3)
δ = 7.65 ꢀ 7.58 (m, 1 H), 7.13 (s, 1 H), 7.03 ꢀ 6.96 (m, 1 H), 6.71 (s, 2 H), 3.93 (s, 3 H), 3.90 (s, 6
H), 1.33 (d like, J = 2.7 Hz, 18 H).
2,6-Di-tert-butyl-4-(3,5-dimethoxybenzylidene)cyclohexa-2,5-dien-1-one (1f):8 After column
purification compound was obtained in 74% yield, (6.6 g). 1H NMR (200MHz, CDCl3) δ = 7.59
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(d like, J = 1.8 Hz, 1 H), 7.13 (s, 1 H), 7.01 (d like, J = 2.0 Hz, 1 H), 6.61 (d like, J = 1.8 Hz, 2
H), 6.55 ꢀ 6.48 (m, 1 H), 3.83 (s, 6 H), 1.32 (d like, J = 4.7 Hz, 18 H).
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2,6-Di-tert-butyl-4-(4-chlorobenzylidene)cyclohexa-2,5-dien-1-one (1g):8 After column
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purification compound was obtained in 62% yield, (5.1 g). H NMR (200MHz , CDCl3) δ =
7.51 ꢀ 7.34 (m, 5 H), 7.12 (s, 1 H), 7.00 (d like J = 2.3 Hz, 1 H), 1.33 (s, 9 H), 1.30 (s, 9 H).
Methyl 4-((3,5-di-tert-butyl-4-oxocyclohexa-2,5-dien-1-ylidene)methyl)benzoate (1h):15
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After column purification compound was obtained in 72% yield, (6.4 g). H NMR (200MHz,
CDCl3) δ = 8.12 (d, J = 8.3 Hz, 2 H), 7.58 ꢀ 7.41 (m, 3 H), 7.18 (s, 1 H), 7.02 (d, J = 2.3 Hz, 1
H), 3.96 (s, 3 H), 1.34 (s, 9 H), 1.29 (s, 9 H).
4-(Benzo[d][1,3]dioxol-4-ylmethylene)-2,6-di-tert-butylcyclohexa-2,5-dien-1-one (1i):8 After
column purification compound was obtained in 68% yield, (5.8 g). 1H NMR (200MHz , CDCl3)
δ = 7.53 (d, J = 2.3 Hz, 1 H), 7.09 (s, 1 H), 7.03 ꢀ 6.95 (m, 3 H), 6.94 ꢀ 6.87 (m, 1 H), 6.05 (s, 2
H), 1.33 (d like, J = 2.5 Hz, 18 H).
2,6-Di-tert-butyl-4-(naphthalen-1-ylmethylene)cyclohexa-2,5-dien-1-one (1j):8 After column
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purification compound was obtained in 63% yield, (5.4 g). H NMR (200MHz , CDCl3) δ =
8.14 ꢀ 8.00 (m, 1 H), 7.98 ꢀ 7.88 (m, 2 H), 7.79 (s, 1 H), 7.66 ꢀ 7.46 (m, 4 H), 7.45 ꢀ 7.36 (m, 1
H), 7.21 (d, J = 1.8 Hz, 1 H), 1.40 (s, 9 H), 1.26 (s, 9 H).
II.
General method for preparation of Secondary Propargylic Acetate (2):
ο
To a stirred solution of alkyne (15 mmol) in freshly dried THF (20 ml) at ꢀ78 C was slowly
added nꢀBuLi (1.6 M solution in hexane, 7.6 mL, 12.2 mmol) under argon atmosphere. The
reaction mixture was stirred at ꢀ78 °C for 30 min and at room temperature for additional 15 min.
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After addition of aldehyde (10 mmol) in 10 mL of THF at ꢀ78 C, the reaction mixture was
allowed to warm up to room temperature gradually, and was stirred for an additional 1h. The
mixture was quenched by sat. solution of NH4Cl and then extracted with ethyl acetate (3 × 20
mL). The combined organic layer was washed with brine, dried over anhydrous Na2SO4 and
concentrated under the reduced pressure to give secondary propargylic alcohol as a colourless
liquid in excellent yields, which was used in subsequent steps without any further purification.
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To a solution of propargyl alcohol (10 mmol) in anhydrous CH2Cl2 (20 mL) was added
Et3N (20 mmol, 2.8 mL, 2 equiv) and catalytic amount of DMAP (0.05 equiv) followed by
addition of acetyl chloride(12 mmol, 0.9 mL, 1.2 equiv)/pivaloyl chloride (12 mmol, 1.5 mL, 1.2
equiv) at 0 °C. The reaction mixture was stirred at room temperature for 2 h. After completion of
the reaction (TLC), the reaction was quenched with ice cold water and mixture was diluted with
CH2Cl2 (25 ml) and washed with 1.0 M aqueous HCl solution (25 mL× 2). Further the organic
layer was sequentially washed with sat. NaHCO3 solution (20 mL × 2), water (20 ml) and sat.
Na2SO4 solution. The combined organic layer was dried over anhydrous Na2SO4 and
concentrated under reduced pressure. The product was purified by flash silica gel column
chromatography using (pet ether /ethyl acetate) as eluent to afford propargylic acetates 2a−2g.
1,3-Diphenylprop-2-yn-1-yl acetate (2a):17 After column purification compound was obtained
in 88% yield, (2.20 g). 1H NMR (200MHz , CDCl3) δ = 7.66 ꢀ 7.58 (m, 2 H), 7.53 ꢀ 7.47 (m, 2
H), 7.46 ꢀ 7.38 (m, 3 H), 7.38 ꢀ 7.30 (m, 3 H), 6.71 (s, 1 H), 2.15 (s, 3 H).
1-(Naphthalen-1-yl)-3-phenylprop-2-yn-1-yl acetate (2b):17 After column purification
compound was obtained in 78% yield, (2.34 g). 1H NMR (200MHz , CDCl3) δ = 8.37 ꢀ 8.29 (m,
1 H), 8.00 ꢀ 7.88 (m, 3 H), 7.67 ꢀ 7.47 (m, 5 H), 7.39 ꢀ 7.29 (m, 4 H), 2.18 (s, 3 H).
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1-(4-(tert-Butyl)phenyl)non-1-yn-3-yl acetate (2c): After column purification compound was
obtained in 69% yield, (2.17 g). IR (CHCl3): νmax = 2956, 2929, 2862, 1741, 1603, 1506, 1461,
1368, 1230, 1115, 1021, 835, 759 cm–1; 1H NMR (200MHz , CDCl3) δ = 7.43 ꢀ 7.29 (m, 4 H),
5.60 (t, J = 6.6 Hz, 1 H), 2.12 (s, 3 H), 1.93 ꢀ 1.76 (m, 2 H), 1.55 ꢀ 1.41 (m, 3 H), 1.31 (s, 14 H),
0.90 (s, 3 H); 13C{1H}NMR (125MHz, CDCl3) δ = 170.1, 151.8, 131.6, 125.2, 119.3, 86.0, 85.3,
64.7, 35.0, 34.8, 31.7, 31.1, 28.8, 25.0, 22.5, 21.1, 14.0; HRMS (ESI-TOF) m/z: [M+Na]+ calcd
for C21H30O2Na 337.2138; found 337.2136.
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1-Phenyloct-2-yn-1-yl acetate (2d): After column purification compound was obtained in 82%
yield, (2.05 g). IR (CHCl3): νmax = 3030, 2932, 2864, 1740, 1456, 1370, 1230, 1144, 1016, 957,
755, 698 cm–1; 1H NMR (400MHz , CDCl3) δ = 7.54 (d, J = 6.1 Hz, 2 H), 7.40 ꢀ 7.33 (m, 3 H),
6.48 (s, 1 H), 2.28 (dt, J = 1.8, 7.3 Hz, 2 H), 2.11 (s, 3 H), 1.60 ꢀ 1.51 (m, 2 H), 1.39 ꢀ 1.31 (m, 4
H), 0.91 (t, J = 7.0 Hz, 3H); 13C{1H}NMR (125MHz ,CDCl3) δ = 169.9, 137.7, 128.7, 128.5,
127.7, 88.4, 76.7, 66.0, 31.0, 28.1, 22.1, 21.1, 18.8, 13.9; HRMS (ESI-TOF) m/z: [M+Na]+
calcd for C16H20O2Na 267.1356; found 267.1349.
4-Phenylbut-3-yn-2-yl acetate (2e):17 After column purification compound was obtained in
84% yield, (1.58 g). 1H NMR (200MHz , CDCl3) δ = 7.49 ꢀ 7.41 (m, 2 H), 7.35 ꢀ 7.28 (m, 3 H),
5.69 (q, J = 6.7 Hz, 1 H), 2.11 (s, 3 H), 1.59 (d, J = 6.7 Hz, 3 H).
4-Methyl-1-phenylpent-1-yn-3-yl acetate (2f):17 After column purification compound was
1
obtained in 76% yield, (1.64 g). H NMR (200MHz , CDCl3) δ = 7.50 ꢀ 7.42 (m, 2 H), 7.36 ꢀ
7.28 (m, 3 H), 5.46 (d, J = 5.6 Hz, 1 H), 2.16 ꢀ 2.12 (m, 3 H), 2.11 ꢀ 1.98 (m, 1 H), 1.08 (t, J =
6.8 Hz, 6 H).
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1,3-Diphenylprop-2-yn-1-yl pivalate (2g):6 After column purification compound was obtained
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in 82% yield, (2.39 g). H NMR (200MHz , CDCl3) δ = 7.59 (dd, J = 1.8, 7.4 Hz, 2 H), 7.53 ꢀ
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7.46 (m, 2 H), 7.44 ꢀ 7.30 (m, 6 H), 6.69 (s, 1 H), 1.26 (s, 9 H).
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III.
(a) General Procedure for Preparation of Primary Propargylic acetate (4):
To a solution of Pd(PPh3)2Cl2 (0.1 mmol, 70.2 mg, 1.0 mol %), CuI (0.2 mmol, 38 mg, 2.0 mol
%) and iodobenzene (10 mmol) in dry degassed Et3N (40 mL) was added propargyl alcohol (0.62
g, 11 mmol, 1.1 equiv) under argon atmosphere. The reaction mixture was stirred at room
temperature until iodobenzene was consumed, as indicated by TLC. The reaction mixture was
filtered through celite, washed with EtOAc, and the combined organic layer was evaporated
under the reduced pressure. The residue was purified by flash silica gel column chromatography
using petroleum ether: EtOAc = 5:1 to 2:1 as an eluent to give the corresponding coupled aryl
propargylic alcohol in good to excellent yields.
To a stirred solution of aryl propargylic alcohol (10.0 mmol), Et3N (7.0 mL, 50.0 mmol, 5
equiv.) and 4ꢀ(dimethylamino)pyridine (DMAP) (127.5 mg, 1.05 mmol) in CH2Cl2 (50 mL) at 0
°C was slowly added acetyl chloride (11 mmol, 0.78 mL, 1.1 equiv.) under argon atmosphere
and the mixture was warmed to room temperature. After stirring for 2 h, the reaction mixture was
quenched with water and extracted with CH2Cl2. The combined organic layer was washed with
1.0 M aqueous solution of HCl and sat. solution of NaHCO3, dried over Na2SO4 and
concentrated under reduced pressure. The obtained residue was purified by silica gel column
chromatography (pet. ether /EtOAc) to afford the pure desired product 4a−4d as colorless oil.
Compound 4e was prepared according to general procedure I as a colourless liquid (1.36 g) in
65% yield.
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3-Phenylprop-2-yn-1-yl acetate (4a):17 After column purification compound was obtained in
73% yield, (1.27 g). 1H NMR (200MHz , CDCl3) δ = 7.54 ꢀ 7.42 (m, 2 H), 7.39 ꢀ 7.27 (m, 3 H),
4.91 (s, 2 H), 2.13 (s, 3 H).
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3-(4-Methoxyphenyl)prop-2-yn-1-yl acetate (4b):17 After column purification compound was
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obtained in 78% yield, (1.60 g). H NMR (200MHz , CDCl3) δ = 7.49 ꢀ 7.33 (m, 2 H), 6.91 ꢀ
6.78 (m, 2 H), 4.90 (s, 2 H), 3.81 (s, 3 H), 2.13 (s, 3 H).
3-(p-Tolyl)prop-2-yn-1-yl acetate (4c):17 After column purification compound was obtained in
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81% yield, (1.52 g). H NMR (200MHz , CDCl3) δ = 7.44 ꢀ 7.29 (m, J = 8.1 Hz, 2 H), 7.20 ꢀ
7.05 (m, J = 7.8 Hz, 2 H), 4.91 (s, 2 H), 2.36 (s, 3 H), 2.14 (s, 3 H).
3-(4-Bromophenyl)prop-2-yn-1-yl acetate (4d): After column purification compound was
obtained in 75% yield, (1.90 g). IR (CHCl3): νmax = 2926, 2857, 1738, 1590, 1481, 1440, 1363,
1249, 1115, 1066, 1025, 820 cm–1; 1H NMR (200MHz , CDCl3) δ = 7.54 ꢀ 7.41 (m, 2 H), 7.39 ꢀ
13
7.28 (m, 2 H), 4.89 (s, 2 H), 2.14 (s, 3 H); C{1H}NMR (125MHz , CDCl3) δ = 170.2, 133.3,
131.6, 123.1, 121.1, 85.3, 84.1, 52.7, 20.7; HRMS (ESI-TOF) m/z: [M+H]+ calcd for
C11H10O2Br 252.9859; found 252.9875.
Undec-2-yn-1-yl acetate (4e): After column purification compound was obtained in 62% yield,
(1.44 g). Rf= 0.72 (pet. ether: ethyl acetate = 9:1); IR (CHCl3): νmax = 2928, 2856, 1749, 1594,
1461, 1377, 1224, 1118, 1025, 771 cm–1; 1HNMR (200MHz , CDCl3) δ =4.66 (t, J = 2.0 Hz, 2
H), 2.27 ꢀ 2.15 (m, 2 H), 2.09 (s, 3 H), 1.60 ꢀ 1.43 (m, 2 H), 1.42 ꢀ 1.24 (m, 10 H), 0.87 (t, J = 6.7
Hz, 3 H); 13C{1H}NMR (50MHz , CDCl3) δ = 170.3, 87.7, 73.8, 52.8, 31.8, 29.1, 29.0, 28.8,
28.4, 22.6, 20.8, 18.7, 14.0; HRMS (ESI-TOF) m/z: [M+Na]+ calcd for C13H22O2Na 233.1512;
found 233.1510.
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IV.
General Procedure for the gold catalyzed reaction: To an oven dried screw cap vial (3
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ml), Ph3PAuCl (0.005 mmol, 2.5 mg, 5 mol %) and AgNTf2 (0.005 mmol, 2 mg, 5 mol %) were
dissolved in 1 ml of moist DCE. The reaction mixture was allowed to stir at room temperature
for 5ꢀ10 min during which solution became turbid (as AgCl was precipitated out) followed by
subsequent addition of pꢀQMs 1 (0.1 mmol, 1 equiv.) and propargylic acetate 2 (0.1 mmol,
1 equiv.). The reaction mixture was stirred in the preheated oil bath at 80 °C and the completion
of the reaction was monitored by TLC. After the completion of reaction, mixture was cooled to
the room temperature, and diluted with ethyl acetate and concentrated under reduced pressure.
The crude product was purified by flash column chromatography using (pet. ether /EtOAc) as
eluent to afford the desired product, diarylmethineꢀsubstituted enones.
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(Z)-2-((3,5-Di-tert-butyl-4-hydroxyphenyl)(phenyl)methyl)-1,3-diphenylprop-2-en-1-one
(3a): After column purification the product was obtained as yellow solid in (47.70 mg, 95%
yield). mp= 73ꢀ75 ºC; Rf= 0.65 (pet. ether : ethyl acetate = 9:1); IR (CHCl3): νmax = 3628, 3013,
2959, 1654, 1591, 1437, 1370, 1231, 1158, 1117, 759, 699 cm–1; 1H NMR (400MHz , CDCl3) δ
= 7.71 (d, J = 7.9 Hz, 2 H), 7.38 (d, J = 7.3 Hz, 2 H), 7.31 (t, J = 7.3 Hz, 3 H), 7.22 (d, J = 6.7
Hz, 1 H), 7.19 ꢀ 7.15 (m, 2 H), 7.09 (s, 2 H), 7.09 ꢀ 7.01 (m, 5 H), 6.57 (s, 1 H), 5.35 (s, 1 H),
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5.06 (s, 1 H), 1.37 (s, 18 H); C{1H}NMR (100MHz , CDCl3) δ = 200.0, 152.4, 144.5, 141.9,
136.1, 136.0, 135.5, 133.3, 132.6, 130.9, 129.5, 128.7, 128.2, 128.0, 127.9, 127.5, 126.5, 126.2,
56.4, 34.3, 30.3; HRMS (ESI-TOF) m/z: [M+Na]+ calcd for C36H38O2Na 525.2764; found
525.2758;
(Z)-2-((3,5-Di-tert-butyl-4-hydroxyphenyl)(p-tolyl)methyl)-1,3-diphenylprop-2-en-1-one
(3b): After column purification the product was obtained as yellow thick liquid (49.54 mg, 96%
yield). Rf= 0.61 (pet. ether : ethyl acetate = 9:1); IR (CHCl3): νmax = 3628, 3013, 2959, 1654,
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1591, 1437, 1370, 1231, 1158, 1117, 759, 699 cm–1; H NMR (400MHz , CDCl3) δ = 7.75 ꢀ
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7.8 Hz, 2 H), 7.10 (s, 2 H), 7.09 ꢀ 7.02 (m, 5 H), 6.58 (s, 1 H), 5.32 (s, 1 H), 5.05 (s, 1 H), 2.33
(s, 3 H), 1.38 (s, 18 H); 13C{1H}NMR (100MHz , CDCl3) δ = 200.0, 152.3, 144.7, 138.9, 136.2,
136.0, 135.9, 135.4, 133.1, 132.6, 131.0, 129.5, 129.3, 129.0, 128.7, 128.0, 127.9, 127.4, 126.1,
56.1, 34.3, 30.3, 21.0; HRMS (ESI-TOF) m/z: [M+Na]+calcd for C37H40O2Na 539.2921; found
539.2916.
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(Z)-2-((3,5-Di-tert-butyl-4-hydroxyphenyl)(4-methoxyphenyl)methyl)-1,3-diphenylprop-2-
en-1-one (3c):After column purification the product was obtained as reddish yellow thick liquid
(48.50 mg, 91% yield); Rf= 0.42 (pet. ether : ethyl acetate = 95:5); IR (CHCl3): νmax = 3623,
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2956, 1653, 1506, 1438, 1239, 1171, 1031, 759, 701 cm–1; H NMR (400MHz , CDCl3) δ =
7.71 (s, 1 H), 7.69 (app. d, J = 1.4 Hz, 1 H), 7.32 ꢀ 7.25 (m, 3 H), 7.19 ꢀ 7.13 (m, 2 H), 7.09 ꢀ
7.01 (m, 7 H), 6.84 (d, J = 8.7 Hz, 2 H), 6.54 (s, 1 H), 5.28 (s, 1 H), 5.04 (s, 1 H), 3.78 (s, 3 H),
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1.36 (s, 18 H); C{1H}NMR (100MHz , CDCl3) δ = 200.1, 158.1, 152.3, 144.8, 136.1, 136.0,
135.5, 134.0, 133.0, 132.6, 131.2, 130.5, 129.5, 128.7, 128.0, 127.9, 127.5, 126.1, 113.6, 55.7,
55.2, 34.3, 30.3; HRMS (ESI-TOF) m/z: [M+H]+ calcd for C37H41O3 533.3050; found
533.3047.
(Z)-2-((3,5-Di-tert-butyl-4-hydroxyphenyl)(3,4-dimethoxyphenyl)methyl)-1,3-diphenylprop-
2-en-1-one (3d): After column purification the product was obtained as reddish brown thick
solid (39.97 mg, 71% yield). mp= 73ꢀ76 ºC; Rf= 0.48 (pet. ether : ethyl acetate = 9:1); IR
(CHCl3): νmax = 3630, 3012, 2957, 1732, 1655, 1592, 1509, 1444, 1232, 1147, 1029, 756, 698
cm–1; 1H NMR (400MHz , CDCl3) δ = 7.74 (d, J = 1.4 Hz, 1 H), 7.72 (d, J = 1.4 Hz, 1 H), 7.32
ꢀ 7.29 (m, 1 H), 7.18 (t, J = 1.4 Hz, 2 H), 7.12 (s, 2 H), 7.10 ꢀ 7.03 (m, 5 H), 6.94 ꢀ 6.90 (m, 2 H),
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6.83 (d, J = 8.2 Hz, 1 H), 6.58 (app. d, J = 1.4 Hz, 1 H), 5.31 (app. d, J = 0.9 Hz, 1 H), 5.08 (s, 1
H), 3.86 (s, 3 H), 3.83 (s, 3 H), 1.39 (s, 18 H); 13C{1H}NMR (100MHz , CDCl3) δ= 200.0,
152.4, 148.6, 147.5, 144.7, 136.0, 135.9, 135.5, 134.3, 133.0, 132.6, 131.0, 129.5, 128.7, 128.0,
127.9, 127.5, 126.0, 121.6, 112.8, 110.8, 56.1, 55.8, 55.7, 34.3, 30.3; HRMS (ESI-TOF) m/z:
[M+H]+ calcd for C38H43O4 563.3156; found 563.3150.
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(Z)-2-((3,5-Di-tert-butyl-4-hydroxyphenyl)(3,4,5-trimethoxy
phenyl)methyl)-1,3-
diphenylprop-2-en-1-one (3e): After column purification the product was obtained as reddish
yellow solid (44.42 mg, 75% yield). mp= 139ꢀ141 ºC; Rf= 0.32 (pet. ether : ethyl acetate =
95:5); IR (CHCl3): νmax = 3632, 3015, 2957, 1655, 1590, 1498, 1432, 1223, 1126, 1029, 759 cm–
1; 1H NMR (400MHz , CDCl3) δ = 7.72 ꢀ 7.69 (m, 2 H), 7.34 ꢀ 7.28 (m, 1 H), 7.19 ꢀ 7.15 (m, 2
H), 7.13 (s, 2 H), 7.10 ꢀ 7.03 (m, 5 H), 6.60 (s, 2 H), 6.59 (app. d, J = 1.4 Hz, 1 H), 5.29 (app. d,
J = 0.9 Hz, 1 H), 5.09 (s, 1 H), 3.82 (s, 3 H), 3.79 (s, 6 H), 1.39 (s, 18 H); 13C{1H}NMR
(100MHz , CDCl3) δ = 200.0, 152.9, 152.5, 144.4, 137.4, 136.4, 136.1, 135.9, 135.6, 133.1,
132.7, 130.6, 129.5, 128.7, 128.0, 127.9, 127.6, 126.1, 106.7, 60.8, 56.7, 56.0, 34.3, 30.3;
HRMS (ESI-TOF) m/z: [M+Na]+ calcd for C39H44O5Na 615.3081; found 615.3073.
(Z)-2-((3,5-Di-tert-butyl-4-hydroxyphenyl)(3,5-dimethoxyphenyl)methyl)-1,3-diphenylprop-
2-en-1-one (3f): After column purification the product was obtained as pale yellow solid (41.03
mg, 73% yield). mp= 74ꢀ76 ºC; Rf= 0.28 (pet. ether : ethyl acetate = 9:1); IR (CHCl3): νmax
=
3638, 3021, 2959, 1654, 1598, 1434, 1216, 1155, 768, 671 cm–1; 1H NMR (500MHz , CDCl3) δ
=7.73 – 7.69 (m, 2 H), 7.32 ꢀ 7.28 (m, 1 H), 7.16 (t, J = 7.6 Hz, 2 H), 7.11 (s, 2 H), 7.09 ꢀ 7.02
(m, 5 H), 6.61 (d like, J = 1.1 Hz, 1 H), 6.54 (d like, J = 2.3 Hz, 2 H), 6.32 (t, J = 2.1 Hz, 1 H),
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5.29 (s, 1 H), 5.05 (s, 1 H), 3.75 (s, 6 H), 1.37 (s, 18 H); C{1H}NMR (100MHz , CDCl3) δ
=199.9, 160.6, 152.5, 144.5, 144.1, 136.1, 136.0, 135.5, 133.5, 132.6, 130.5, 129.6, 128.8, 128.0,
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127.9, 127.5, 126.1, 107.8, 98.5, 56.6, 55.2, 34.3, 30.3; HRMS (ESI-TOF) m/z: [M+H]+ calcd
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for C38H43O4 563.3156; found 563.3151.
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(Z)-2-((3,5-Di-tert-butyl-4-hydroxyphenyl)(naphthalen-1-yl)methyl)-1,3-diphenylprop-2-en-
1-one (3g): After column purification the product was obtained as pale yellow solid (51.33 mg,
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93% yield). mp= 144ꢀ146 ºC; Rf= 0.52 (pet. ether : ethyl acetate = 95:5); IR (CHCl3): νmax
=
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3635, 3017, 2959, 1647, 1437, 1221, 1160, 758, 700 cm–1; H NMR (400MHz , CDCl3) δ =
8.58 (d, J = 8.2 Hz, 1 H), 7.85 (dd, J = 1.4, 8.2 Hz, 1 H), 7.77 ꢀ 7.72 (m, 3 H), 7.60 ꢀ 7.56 (m, 1
H), 7.50 ꢀ 7.46 (m, 1 H), 7.45 ꢀ 7.40 (m, 1 H), 7.30 (d, J = 7.8 Hz, 1 H), 7.25 (s, 2 H), 7.13 (t, J =
7.8 Hz, 2 H), 7.01 ꢀ 6.94 (m, 6 H), 6.51 (app. d, J = 1.4 Hz, 1 H), 6.23 (s, 1 H), 5.09 (s, 1 H),
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1.41 (s, 18 H); C{1H}NMR (100MHz , CDCl3) δ = 200.1, 152.6, 143.9, 138.8, 136.2, 135.6,
134.6, 134.0, 132.5, 131.9, 129.7, 129.7, 128.7, 128.5, 127.9, 127.7, 127.4, 126.7, 126.3, 125.5,
125.1, 124.6, 52.5, 34.4, 30.3; HRMS (ESI-TOF) m/z: [M+Na]+ calcd for C40H40O2Na
575.2921; found 575.2919.
Methyl (Z)-4-(2-benzoyl-1-(3,5-di-tert-butyl-4-hydroxy phenyl)-3-phenylallyl)benzoate (3h):
After column purification the product was obtained as yellow thick liquid (40.41 mg, 74%
yield). Rf= 0.26 (pet. ether : ethyl acetate = 95:5); IR (CHCl3): νmax = 3628, 2956, 1719 1655,
1604, 1438, 1280, 1225, 1111, 769 cm–1; 1H NMR (400MHz , CDCl3) δ = 7.99 (d, J = 8.2 Hz, 2
H), 7.70 (dd, J = 1.4, 8.2 Hz, 2 H), 7.46 (d, J = 8.2 Hz, 2 H), 7.35 ꢀ 7.30 (m, 1 H), 7.20 ꢀ 7.15 (m,
2 H), 7.09 ꢀ 7.07 (m, 4 H), 7.06 (s, 2 H), 7.05 ꢀ 7.04 (m, 1 H), 6.57 (app. d, J = 1.4 Hz, 1 H), 5.39
(s, 1 H), 5.09 (s, 1 H), 3.90 (s, 3 H), 1.36 (s, 18 H); 13C{1H}NMR (100MHz , CDCl3) δ = 199.7,
167.1, 152.6, 147.5, 143.6, 136.0, 135.7, 135.6, 133.9, 132.8, 130.2, 129.6, 129.5, 129.4, 128.7,
128.4, 128.1, 128.0, 127.7, 126.1, 56.4, 52.0, 34.3, 30.2; HRMS (ESI-TOF) m/z: [M+H]+ calcd
for C37H39O4 547.2843; found 547.2839.
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(Z)-2-((4-Chlorophenyl)(3,5-di-tert-butyl-4-hydroxyphenyl)methyl)-1,3-diphenylprop-2-en-
1-one (3i): After column purification the product was obtained as pale yellow solid (46.65 mg,
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87% yield). mp= 143ꢀ145 ºC; Rf= 0.48 (pet. ether : ethyl acetate = 95:5); IR (CHCl3): νmax
=
9
3631, 3016, 2958, 1652, 1591, 1482, 1433, 1225, 1020, 757 cm–1;1H NMR (400MHz , CDCl3) δ
= 7.70 (dd, J = 1.4, 8.2 Hz, 2 H), 7.35 ꢀ 7.27 (m, 6 H), 7.21 ꢀ 7.16 (m, 2 H), 7.10 ꢀ 7.07 (m, 4 H),
7.06 (s, 2 H), 6.57 (aap. d, J = 1.4 Hz, 1 H), 5.31 (s, 1 H), 5.09 (s, 1 H), 1.37 (s, 18 H);
13C{1H}NMR (100MHz , CDCl3) δ = 199.8, 152.6, 143.9, 140.6, 136.0, 135.7, 133.6, 132.8,
132.2, 130.8, 130.4, 129.5, 128.7, 128.4, 128.1, 128.0, 127.7, 126.0, 55.9, 34.3, 30.2; HRMS
(ESI-TOF) m/z: [M+Na]+ calcd for C36H37ClO2Na 559.2374; found 559.2373.
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(Z)-2-(Benzo[d][1,3]dioxol-5-yl(3,5-di-tert-butyl-4-hydroxyphenyl)methyl)-1,3-
diphenylprop-2-en-1-one (3j): After column purification the product was obtained as reddish
brown thick liquid (44.80 mg, 82% yield); Rf= 0.40 (pet. ether : ethyl acetate = 95:5); IR
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(CHCl3): νmax = 3634, 3016, 2959, 1655, 1592, 1488, 1437, 1227, 1039, 760 cm–1; H NMR
(400MHz , CDCl3) δ = 7.74 ꢀ 7.70 (m, 2 H), 7.35 ꢀ 7.30 (m, 1 H), 7.19 (t, J = 7.8 Hz, 2 H), 7.10
ꢀ 7.03 (m, 7 H), 6.88 ꢀ 6.82 (m, 2 H), 6.76 (d, J = 8.2 Hz, 1 H), 6.59 (app. d, J = 0.9 Hz, 1 H),
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5.94 (s, 2 H), 5.27 (s, 1 H), 5.07 (s, 1 H), 1.38 (s, 18 H); C{1H}NMR (100MHz , CDCl3) δ =
199.9, 152.4, 147.5, 146.1, 144.5, 136.1, 136.0, 135.9, 135.6, 133.3, 132.6, 130.9, 129.5, 128.7,
128.0, 127.9, 127.5, 126.0, 122.6, 110.0, 108.0, 100.9, 56.1, 34.3, 30.3; HRMS (ESI-TOF) m/z:
[M+H]+ calcd for C37H37O4 547.2843; found 547.2839.
(Z)-2-((4-Chlorophenyl)(3,5-di-tert-butyl-4-hydroxyphenyl)methyl)-1-phenylbut-2-en-1-one
(3k): After column purification the product was obtained as yellow solid (34.62 mg, 73% yield).
mp= 96ꢀ99 ºC; Rf= 0.45 (pet. ether : ethyl acetate = 95:5); IR (CHCl3): νmax = 3633, 2958, 1722,
1657, 1437, 1235, 1156, 758 cm–1; 1H NMR (400MHz , CDCl3) δ = 7.81 ꢀ 7.78 (m, 2 H), 7.53 ꢀ
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1 H), 5.15 (s, 1 H), 5.06 (s, 1 H), 1.56 (dd, J = 1.4, 7.3 Hz, 3 H), 1.37 (s, 18 H); C{1H}NMR
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(100MHz , CDCl3) δ = 199.5, 152.5, 143.7, 141.0, 137.6, 135.7, 133.0, 132.1, 131.2, 130.8,
130.1, 129.3, 128.5, 128.4, 126.0, 55.0, 34.4, 30.4, 16.1; HRMS (ESI-TOF) m/z: [M+Na]+ calcd
for C31H35ClO2Na 497.2218; found 497.2214.
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Methyl(Z)-4-(2-benzoyl-1-(3,5-di-tert-butyl-4-hydroxy phenyl)but-2-en-1-yl)benzoate (3l):
After column purification the product was obtained as pale yellow thick liquid (44.32 mg, 89%
yield). Rf= 0.42 (pet. ether : ethyl acetate = 95:5); IR (CHCl3): νmax = 3628, 2957, 1769, 1655,
1437, 1280, 1238, 1111, 759 cm–1; 1H NMR (400MHz , CDCl3) δ = 7.97 (d, J = 8.2 Hz, 2 H),
7.82 ꢀ 7.78 (m, 2 H), 7.51 (t, J = 7.3 Hz, 1 H), 7.42 ꢀ 7.36 (m, 4 H), 6.98 (s, 2 H), 5.61 ꢀ 5.56 (m,
1 H), 5.24 (s, 1 H), 5.07 (s, 1 H), 3.90 (s, 3 H), 1.57 (dd, J = 0.9, 7.3 Hz, 3 H), 1.36 (s, 18 H);
13C{1H}NMR (100MHz , CDCl3) δ = 199.3, 167.1, 152.4, 147.8, 143.4, 137.5, 135.6, 132.9,
130.8, 130.4, 129.5, 129.4, 129.2, 128.4, 128.2, 126.0, 55.5, 52.0, 34.3, 30.2, 16.1; HRMS (ESI-
TOF) m/z: [M+H]+ calcd for C33H39O4 499.2843; found 499.2836.
(Z)-2-((3,5-Di-tert-butyl-4-hydroxyphenyl)(phenyl)methyl)-4-methyl-1-phenylpent-2-en-1-
one (3m): After column purification the product was obtained as yellow solid (39.34 mg, 84%
yield). mp= 120ꢀ122 ºC; Rf= 0.48 (pet. ether : ethyl acetate = 95:5); IR (CHCl3): νmax = 3635,
1
3017, 2959, 1647, 1437, 1221, 1160, 758, 700 cm–1; H NMR (400MHz , CDCl3) δ = 7.78 ꢀ
7.74 (m, 2 H), 7.50 ꢀ 7.45 (m, 1 H), 7.38 ꢀ 7.33 (m, 2 H), 7.29 ꢀ 7.26 (m, 1 H), 7.26 ꢀ 7.22 (m, 3
H), 7.20 ꢀ 7.15 (m, 1 H), 6.99 (s, 2 H), 5.26 (dd, J = 1.4, 10.5 Hz, 1 H), 5.08 (s, 1 H), 5.03 (s, 1
H), 2.30 ꢀ 2.20 (m, 1 H), 1.35 (s, 18 H), 0.87 (d, J = 6.4 Hz, 3 H), 0.83 (d, J = 6.4 Hz, 3 H);
13C{1H}NMR (100MHz , CDCl3) δ = 199.7, 152.2, 142.4, 141.6, 140.8, 137.7, 135.3, 132.7,
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131.3, 129.4, 129.1, 128.2, 128.1, 126.2, 126.1, 55.0, 34.3, 30.3, 29.0, 22.6, 22.5; HRMS (ESI-
TOF) m/z: [M+Na]+ calcd for C33H40O2Na 491.2921; found 491.2915.
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phenylprop-2-en-1-one (3n): After column purification the product was obtained as reddish
brown thick liquid (43.60 mg, 79% yield); Rf= 0.52 (pet. ether : ethyl acetate = 95:5); IR
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(CHCl3): νmax = 3629, 2957, 1653, 1592, 1437, 1234, 1157, 1115, 766,705 cm–1; H NMR
(400MHz , CDCl3) δ = 7.89 (d, J = 8.2 Hz, 1 H), 7.71 (d, J = 7.8 Hz, 1 H), 7.58 ꢀ 7.55 (m, 2 H),
7.54 ꢀ 7.51 (m, 1 H), 7.50 ꢀ 7.45 (m, 4 H), 7.38 ꢀ 7.34 (m, 2 H), 7.26 (s, 2 H), 7.24 ꢀ 7.21 (m, 1
H), 7.18 ꢀ 7.13 (m, 2 H), 7.11 ꢀ 7.05 (m, 2 H), 6.93 ꢀ 6.87 (m, 2 H), 5.58 (s, 1 H), 5.11 (s, 1 H),
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1.43 (s, 18 H); C{1H}NMR (100MHz , CDCl3) δ = 199.4, 152.5, 146.7, 142.2, 136.8, 135.7,
133.7, 133.0, 132.9, 132.1, 131.2, 131.1, 129.4, 128.8, 128.5, 128.4, 128.2, 127.5, 127.4, 126.5,
126.2, 126.1, 125.7, 125.0, 124.2, 55.8, 34.4, 30.3; HRMS (ESI-TOF) m/z: [M+H]+ calcd for
C40H41O2 553.3101; found 553.3098.
(Z)-1-(4-(tert-Butyl)phenyl)-2-((3,5-di-tert-butyl-4-hydroxyphenyl)(phenyl)methyl)non-2-en-
1-one (3o): After column purification the product was obtained as yellow thick liquid (41.91
mg, 74% yield). Rf= 0.67 (pet. ether : ethyl acetate = 95:5); IR (CHCl3): νmax = 3638, 2958,
2865, 1725, 1656, 1605, 1444, 1238, 1157, 1113, 759, 703 cm–1; 1H NMR (400MHz , CDCl3) δ
= 7.74 (d, J = 8.2 Hz, 2 H), 7.39 (d, J = 8.7 Hz, 2 H), 7.30 (d, J = 4.6 Hz, 4 H), 7.23 ꢀ 7.17 (m, 1
H), 7.00 (s, 2 H), 5.47 ꢀ 5.41 (m, 1 H), 5.17 (s, 1 H), 5.03 (s, 1 H), 1.94 ꢀ 1.87 (m, 2 H), 1.37 (s,
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18 H), 1.33 (s, 9 H), 1.27 ꢀ 1.11 (m, 8 H), 0.83 (t, J = 7.1 Hz, 3 H); C{1H}NMR (100MHz ,
CDCl3) δ = 199.4, 156.4, 152.3, 143.3, 142.6, 135.4, 135.1, 135.0, 131.7, 130.4, 129.5, 129.3,
128.9, 128.2, 126.3, 126.2, 125.3, 55.5, 35.1, 34.4, 31.6, 31.2, 30.4, 30.0, 29.7, 29.6, 29.4, 28.8,
22.6, 14.1; HRMS (ESI-TOF) m/z: [M+Na]+ calcd for C40H54O2Na 589.4016; found 589.4014.
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(Z)-2-((3,5-Di-tert-butyl-4-hydroxyphenyl)(phenyl)methyl) -1-phenyloct-1-en-3-one (3p):
After column purification the product was obtained as pale yellow solid (38.68 mg, 78% yield).
mp= 85ꢀ87 ºC; Rf= 0.57 (pet. ether : ethyl acetate = 95:5); IR (CHCl3): νmax = 3636, 3016,
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2957, 2869, 1680, 1438, 1227, 1154, 758, 701 cm–1; H NMR (400MHz , CDCl3) δ = 7.34 ꢀ
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7.28 (m, 6 H), 7.26 ꢀ 7.20 (m, 2 H), 7.17 ꢀ 7.14 (m, 2 H), 7.08 (s, 2 H), 6.29 (s, 1 H), 5.27 (s, 1
H), 5.12 (s, 1 H), 2.07 ꢀ 1.91 (m, 2 H), 1.41 (s, 18 H), 1.23 ꢀ 1.19 (m, 2 H), 1.04 ꢀ 0.99 (m, 2 H),
0.87 ꢀ 0.84 (m, 2 H), 0.71 (t, J = 7.3 Hz, 3 H); 13C{1H}NMR (100MHz , CDCl3) δ = 210.6,
152.5, 149.0, 141.7, 136.7, 135.6, 131.6, 130.6, 129.5, 129.0, 128.9, 128.3, 128.2, 127.9, 127.8,
126.5, 126.1, 55.5, 43.8, 34.4, 30.9, 30.3, 23.3, 22.2, 13.8; HRMS (ESI-TOF) m/z: [M+H]+
calcd for C35H45O2497.3414; found 497.3407.
(Z)-2-((4-Hydroxy-3,5-dimethylphenyl)(phenyl)methyl)-1,3-diphenylprop-2-en-1-one (3q):
After column purification the product was obtained as pale yellow thick liquid (31.36 mg, 75%
yield). Rf= 0.52 (pet. ether : ethyl acetate = 9:1); IR (CHCl3): νmax = 3455, 3062, 3020, 2922,
2858, 1647, 1590, 1485, 1447, 1219, 1022, 758 cm–1; 1H NMR (500MHz , CDCl3) δ = 7.78 (d,
J = 7.6 Hz, 2 H), 7.36 ꢀ 7.29 (m, 5 H), 7.25 ꢀ 7.21 (m, 3 H), 7.11 ꢀ 7.03 (m, 5 H), 6.93 (s, 2 H),
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6.54 (s, 1 H), 5.32 (s, 1 H), 4.58 (br. s., 1 H), 2.19 (s, 6 H): C{1H}NMR (125MHz , CDCl3) δ
= 199.8, 151.0, 144.1, 141.5, 136.0, 135.8, 133.9, 132.7, 132.2, 129.7, 129.6, 129.5, 128.8,
128.4, 128.1, 128.0, 127.6, 126.6, 122.9, 55.5, 16.0; HRMS (ESI-TOF) m/z: [M+Na]+ calcd for
C30H26O2Na 441.1825; found 441.1818.
2-((3,5-Di-tert-butyl-4-hydroxyphenyl)(phenyl)methyl)-1-phenylprop-2-en-1-one (5a): After
column purification the product was obtained as reddish brown solid (36.64 mg, 86% yield).
mp= 130ꢀ132 ºC; Rf= 0.62 (pet. ether : ethyl acetate = 95:5); IR (CHCl3): νmax = 3630, 2958,
1656, 1437,1316, 1214, 1156, 757, 699 cm–1; 1H NMR (400MHz , CDCl3) δ = 7.84 ꢀ 7.80 (m, 2
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H), 7.56 ꢀ 7.50 (m, 1 H), 7.46 ꢀ 7.41 (m, 2 H), 7.34 ꢀ 7.27 (m, 3 H), 7.27 ꢀ 7.25 (m, 1 H), 7.23 ꢀ
7.18 (m, 1 H), 7.05 (s, 2 H), 5.85 (s, 1 H), 5.63 (s, 1 H), 5.48 (app. d, J = 0.9 Hz, 1 H), 5.08 (s, 1
H), 1.40 (s, 18 H); 13C{1H}NMR (100MHz , CDCl3) δ = 197.1, 152.3, 151.8, 142.2, 137.6,
135.6, 132.3, 131.5, 129.7, 129.2, 128.3, 128.1, 127.5, 126.3, 125.8, 52.2, 34.4, 30.3; HRMS
(ESI-TOF) m/z: [M+H]+ calcd for C30H35O2 427.2632; found 427.2623.
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2-((3,5-Di-tert-butyl-4-hydroxyphenyl)(p-tolyl)methyl)-1-phenylprop-2-en-1-one (5b): After
column purification the product was obtained as reddish brown solid (37.42 mg, 85% yield).
mp= 131ꢀ132 ºC; Rf= 0.57 (pet. ether : ethyl acetate = 95: 5); IR (CHCl3): νmax = 3637, 3017,
2960, 1655, 1437, 1217, 1156, 759 cm–1; 1H NMR (400MHz , CDCl3) δ = 7.82 (d, J = 7.3 Hz, 2
H), 7.56 ꢀ 7.50 (m, 1 H), 7.43 (t, J = 7.3 Hz, 2 H), 7.14 (q, J = 8.2 Hz, 4 H), 7.05 (s, 2 H), 5.82 (s,
1 H), 5.59 (s, 1 H), 5.48 (s, 1 H), 5.07 (s, 1 H), 2.32 (s, 3 H), 1.40 (s, 18 H); 13C{1H}NMR
(100MHz , CDCl3) δ = 197.2, 152.3, 151.9, 139.2, 137.6, 135.8, 135.5, 132.2, 131.6, 129.7,
129.1, 129.0, 128.1, 127.2, 125.7, 51.9, 34.3, 30.3, 21.0; HRMS (ESI-TOF) m/z: [M+H]+ calcd
forC31H37O2 441.2788; found 441.2780.
2-((3,5-Di-tert-butyl-4-hydroxyphenyl)(4-methoxyphenyl) methyl)-1-phenylprop-2-en-1-one
(5c): After column purification the product was obtained as reddish yellow thick liquid (38.78
mg, 85% yield). Rf= 0.42 (pet. ether : ethyl acetate = 95:5); IR (CHCl3): νmax = 3632, 2959,
1655, 1606, 1440, 1217, 1168, 759 cm–1; 1H NMR (400MHz , CDCl3) δ = 7.83 ꢀ 7.80 (m, 2 H),
7.55 ꢀ 7.50 (m, 1 H), 7.45 ꢀ 7.40 (m, 2 H), 7.17 (d, J = 8.2 Hz, 2 H), 7.04 (s, 2 H), 6.85 (d, J = 8.7
Hz, 2 H), 5.81 (s, 1 H), 5.57 (s, 1 H), 5.47 (app. d, J = 0.9 Hz, 1 H), 5.06 (s, 1 H), 3.79 (s, 3 H),
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1.39 (s, 18 H); C{1H}NMR (100MHz , CDCl3) δ = 197.2, 158.0, 152.3, 152.0, 137.6, 135.6,
134.3, 132.2, 131.8, 130.1, 129.7, 128.1, 127.1, 125.6, 113.7, 55.2, 51.5, 34.3, 30.3; HRMS
(ESI-TOF) m/z: [M+Na]+calcd for C31H36O3Na 479.2557; found 479.2548.
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2-((3,5-Di-tert-butyl-4-hydroxyphenyl)(3,4,5-trimethoxy
phenyl)methyl)-1-phenylprop-2-
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en-1-one (5d): After column purification the product was obtained as pale yellow solid (39.75
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mg, 77% yield). mp= 133ꢀ135 ºC; Rf= 0.30 (pet. ether : ethyl acetate = 8:2); IR (CHCl3): νmax
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3627, 2955, 1656, 1589, 1431, 1324, 1238, 1004, 757 cm–1; H NMR (400MHz , CDCl3) δ =
7.85 ꢀ 7.81 (m, 2 H), 7.57 ꢀ 7.51 (m, 1 H), 7.46 ꢀ 7.41 (m, 2 H), 7.07 (s, 2 H), 6.49 (s, 2 H), 5.83
(s, 1 H), 5.54 (s, 1 H), 5.49 (app. d, J = 0.9 Hz, 1 H), 5.10 (s, 1 H), 3.81 (s, 3 H), 3.80 (s, 6 H),
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1.41 (s, 18 H); C{1H}NMR (100MHz , CDCl3) δ = 197.1, 153.0, 152.4, 151.6, 137.7, 137.4,
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136.4, 135.7, 132.4, 131.1, 129.7, 128.2, 127.1, 125.7, 106.3, 60.8, 56.0, 52.5, 34.4, 30.3;
HRMS (ESI-TOF) m/z: [M+Na]+ calcd for C33H40O5Na 539.2768; found 539.2759.
2-((4-Chlorophenyl)(3,5-di-tert-butyl-4-hydroxyphenyl)methyl)-1-phenylprop-2-en-1-one
(5e): After column purification the product was obtained as reddish brown solid (37.75 mg, 82%
yield). mp= 132ꢀ133 ºC; Rf= 0.43 (pet. ether : ethyl acetate = 95:9); IR (CHCl3): νmax =3632,
3069, 2958, 1656, 1483, 1437, 1240, 1156, 980, 754, 703 cm–1; 1H NMR (400MHz , CDCl3) δ
= 7.82 ꢀ 7.79 (m, 2 H), 7.56 ꢀ 7.51 (m, 1 H), 7.46 ꢀ 7.41 (m, 2 H), 7.28 (d, J = 8.7 Hz, 2 H), 7.19
(d, J = 8.7 Hz, 2 H), 7.01 (s, 2 H), 5.86 (s, 1 H), 5.60 (s, 1 H), 5.48 (d like, J = 1.4 Hz, 1 H), 5.10
(s, 1 H), 1.39 (s, 18 H); 13C{1H}NMR (100MHz , CDCl3) δ = 196.9, 152.5, 151.3, 140.9, 137.4,
135.8, 132.4, 132.1, 131.0, 130.5, 129.7, 128.5, 128.2, 127.7, 125.6, 51.6, 34.4, 30.3; HRMS
(ESI-TOF) m/z: [M+H]+calcd for C30H34ClO2 461.2242; found 461.2233.
Methyl 4-(2-benzoyl-1-(3,5-di-tert-butyl-4-hydroxy phenyl)allyl)benzoate (5f): After column
purification the product was obtained as pale yellow solid (36.34 mg, 75% yield). mp= 150ꢀ154
ºC; Rf= 0.45 (pet. ether : ethyl acetate = 9:1); IR (CHCl3): νmax = 3631, 2957, 1719, 1657, 1608,
1437, 1280, 1112, 757, 703 cm–1; H NMR (400MHz , CDCl3) δ = 7.99 (d, J = 8.2 Hz, 2 H),
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2 H), 5.89 (s, 1 H), 5.68 (s, 1 H), 5.48 (app. d, J = 1.4 Hz, 1 H), 5.11 (s, 1 H), 3.90 (s, 3 H), 1.39
(s, 18 H); 13C{1H}NMR (100MHz , CDCl3) δ = 196.8, 167.0, 152.6, 151.0, 147.8, 137.4, 135.8,
132.4, 130.7, 129.7, 129.7, 129.2, 128.3, 128.2, 128.1, 125.7, 52.2, 52.0, 34.4, 30.3; HRMS
(ESI-TOF) m/z: [M+H]+calcd for C32H37O4 485.2686; found 485.2677.
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2-((2-Bromophenyl)(3,5-di-tert-butyl-4-hydroxyphenyl) methyl)-1-phenylprop-2-en-1-one
(5g): Compound 5g was prepared according to general procedure I. After column purification the
product was obtained as yellow solid (43.35 mg, 86% yield). mp= 137ꢀ139 ºC; Rf= 0.57 (pet.
ether : ethyl acetate = 95:5); IR (CHCl3): νmax = 3633, 2959, 1657, 1435, 1237, 1157, 756, 701
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cm–1; H NMR (400MHz , CDCl3) δ = 7.84 ꢀ 7.81 (m, 2 H), 7.61 ꢀ 7.57 (m, 1 H), 7.56 ꢀ 7.51
(m, 1 H), 7.46 ꢀ 7.41 (m, 2 H), 7.27 ꢀ 7.21 (m, 1 H), 7.11 ꢀ 7.06 (m, 2 H), 7.05 (s, 2 H), 5.96 (s, 1
H), 5.92 (s, 1 H), 5.44 (d like, J = 1.4 Hz, 1 H), 5.10 (s, 1 H), 1.40 (s, 18 H); 13C{1H}NMR
(50MHz , CDCl3) δ = 196.4, 152.6, 149.9, 142.3, 137.6, 135.7, 133.1, 132.2, 130.6, 130.0,
129.6, 128.3, 128.1, 127.9, 127.1, 126.0, 125.5, 51.9, 34.4, 30.3; HRMS (ESI-TOF) m/z:
[M+H]+ calcd for C30H34BrO2 505.1737; found 505.1729.
2-((3,5-Di-tert-butyl-4-hydroxyphenyl)(naphthalen-1-yl)methyl)-1-phenylprop-2-en-1-one
(5h): Compound 5h was prepared according to general procedure I. After column purification
the product was obtained as yellow solid (41.92 mg, 88% yield). mp= 145ꢀ147 ºC; Rf= 0.55 (pet.
ether : ethyl acetate = 95:5); IR (CHCl3): νmax = 3634, 3010, 2960, 1654, 1436, 1220, 1157, 758
cm–1; 1H NMR (400MHz , CDCl3) δ = 8.26 (d, J = 8.2 Hz, 1 H), 7.90 ꢀ 7.85 (m, 3 H), 7.75 (d, J
= 8.2 Hz, 1 H), 7.57 ꢀ 7.49 (m, 3 H), 7.47 ꢀ 7.43 (m, 2 H), 7.43 ꢀ 7.37 (m, 1 H), 7.16 (s, 2 H),
7.10 (d, J = 7.3 Hz, 1 H), 6.43 (s, 1 H), 5.80 (s, 1 H), 5.33 (s, 1 H), 5.11 (s, 1 H), 1.42 (s, 18 H);
13C{1H}NMR (100MHz , CDCl3)δ = 197.0, 152.6, 150.8, 139.3, 137.4, 135.7, 133.9, 132.4,
131.9, 131.7, 130.4, 129.9, 128.5, 128.3, 128.1, 127.8, 127.2, 127.1, 126.3, 126.2, 125.5, 125.2,
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