Palladium-catalyzed aerobic oxidative coupling of allylic alcohols with anilines in the synthesis of nitrogen heterocycles

Article abstract of DOI:10.1021/acs.joc.8b00287

We report herein an unprecedented and expedient Pd-catalyzed oxidative coupling of allyl alcohols with anilines to afford β-amino ketones which are converted into substituted quinolines in a one-pot fashion. The exclusive preference for N-alkylation over N-allylation makes this approach unique when compared to those reported in literature. Detailed mechanistic investigations reveal that the conjugate addition pathway was the predominant one over the allylic amination pathway. The notable aspects of the present approach are the use of readily available, bench-stable allyl alcohols and molecular oxygen as the terminal oxidant, in the process dispensing the need for unstable and costly enones. Further, we explored the synthetic utility of β-amino ketones through an intramolecular α-arylation methodology and a one-pot domino annulation, thereby providing rapid access to indolines and quinolines.

Full text of DOI:10.1021/acs.joc.8b00287

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Palladium-Catalyzed Aerobic Oxidative Coupling of Allylic
Alcohols with Anilines in the Synthesis of Nitrogen Heterocycles
Gangam Srikanth Kumar, Diksha Singh, Manish Kumar, and Manmohan Kapur
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b00287 • Publication Date (Web): 13 Mar 2018
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Palladium-Catalyzed Aerobic Oxidative Coupling of
Allylic Alcohols with Anilines in the Synthesis of
Nitrogen Heterocycles
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Gangam Srikanth Kumar, Diksha Singh, Manish Kumar and Manmohan Kapur*
Department of Chemistry, Indian Institute of Science Education and Research Bhopal, Bhopal
Bypass Road, Bhauri, Bhopal 462066, MP, India
E-mail: mk@iiserb.ac.in
ABSTRACT: We report herein, an unprecedented and expedient Pd-catalyzed oxidative
coupling of allyl alcohols with anilines to afford amino ketones which are converted into
substituted quinolines in a one-pot fashion. The exclusive preference for N-alkylation over N-
allylation makes this approach unique, when compared to those reported in literature. Detailed
mechanistic investigations reveal that the conjugate addition pathway was the predominant
one over the allylic amination pathway. The notable aspects of the present approach are the
use of readily available, bench-stable, allyl alcohols and molecular oxygen as the terminal
oxidant, in the process dispensing the need for unstable and costly enones. Further, we
explored the synthetic utility of amino ketones through an intramolecular arylation
methodology and a one-pot domino annulation thereby providing rapid access to indolines
and quinolines.
INTRODUCTION
Allylic alcohols, which possess unique reactivity, have emerged as valuable building blocks
for organic synthesis in the construction of complex entities.1 This is due to the fact that allyl
alcohols can react as allylating as well as alkylating agents to afford diverse products. Allyl
alcohols often function as an alternative to unsaturated carbonyl compounds and
preactivated allylating agents.2 The palladium-catalyzed Mizoroki-Heck reaction has also
been extended to non-biased olefins and allylic alcohols as coupling partners, and the cross-
coupling of various arylating agents with allylic alcohols have been extensively studied.3 This
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method has advantages in accessing aryl carbonyl compounds since it avoids the use of
highly electrophilic agents such as vinyl ketones and alkyl halides. Notable works by the
groups of Sigman, Jiang, Lei and Kommu, among others, have made considerable
contributions to this field.4-6 Transition metal-mediated oxidation of alcohols to carbonyl
compounds has revolutionized the approaches in the organic chemistry, thereby making
alcohols important building blocks in synthesis.7 Palladium-catalyzed oxidation of alcohols
has witnessed important advancements and alcohols are now widely used as efficient
alternatives to carbonyl compounds. In this context, the metal-catalyzed oxidative coupling of
allylic alcohols with anilines would be a straightforward approach to access amino
carbonyl compounds. To the best of our knowledge, the palladium-mediated oxidative
coupling of allyl alcohols with anilines to directly afford amino ketones in one step has not
been studied. The direct coupling of amines and allylic alcohols provides N-allylated products
via allylic amination reaction (Scheme 1),8 which is the reason why allylic alcohols have not
been used in the synthesis of aminoketones. With advancements in the Tsuji-Trost
allylation,1c direct activation of allylic alcohols leading to the electrophilic allyl
intermediates, is a significant advancement in the area of nucleophilic allylation reactions.
Moreover, considerable progress has been achieved in the transition metal catalyzed direct
coupling of anilines with allyl alcohols to afford quinolines as the products.9 Very recently,
we reported a ruthenium-catalyzed [3+3] annulation of anilines with allyl alcohols for the
synthesis of substituted quinolines (Scheme 1).10 With our continued interest in exploring the
reactivity of allyl alcohols,10, 11 we report herein, an efficient and unprecedented palladium-
catalyzed oxidative coupling of allyl alcohols with anilines to directly access amino
ketones. We also extended the synthetic utility of amino ketones via an intramolecular
arylation methodology and a one-pot domino annulation thereby providing rapid access to
indolines and quinolines.
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Scheme 1: Palladium catalyzed aerobic oxidative coupling of allylic alcohols with amines.
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The synthesis of aminocarbonyl compounds have attracted great attention of chemists due
to their pervasiveness as fundamental building blocks for biologically essential scaffolds. In
particular, amino ketones serve as the critical intermediates for the synthesis of amino
acids, lactam antibiotics and diverse nitrogen heterocycles.12 The aza-Michael reaction is
one of the most utilized approach for the synthesis of the aminocarbonyl compounds which
involves a conjugate addition of amines on to unsaturated olefins.13-17 Numerous
protocols, using stoichiometric or catalytic amounts of Lewis acids15 and transition metal
catalysts16 as well as organocatalysts17 have been reported. Despite significant advances,
there are still limitations for these approaches as the most of these methods often involve the
use of strongly acidic or basic conditions which can cause polymerization of labile
unsaturated carbonyl compounds in addition to long reaction times. To circumvent these
challenges, the development of simple, convenient approaches for the synthesis of
aminoketones is highly desirable. In this regard, use of allyl alcohols as an alternative to
the labile vinyl ketones can be a highly user-friendly approach for the synthesis of
aminoketones. During the preparation of our manuscript, Jiang and co-workers reported a
novel Pd-catalyzed oxidative amination of homoallylic alcohols to afford β-amino ketones by
using TBHP as the terminal oxidant, but the scope of this methodology was limited to only a
single homoallylic alcohol.18 The mechanism proposed involved the TBHP mediated Wacker-
type oxidation of homoallylic alcohol to form 4-hydroxybutan-2-one and followed by
hydride elimination and condensation reaction with amine to afford the product.
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RESULTS AND DISCUSSION
We began our optimization studies by choosing aniline and but-3-en-2-ol as the benchmark
substrates for the transformation. The most important results are summarized in Table 1 (for
detailed optimization studies, see the Supporting Information (SI)). Various catalytic systems
were screened, in which an initial success was obtained (20% yield, Table 1, entry 4), under
palladium catalysis. Increasing the loading of Cu(OAc)2 did not result in any significant
increment in the yield (Table 1, entry 5). The desired product was obtained in 30% yield
when the acetate source was changed (Table 1, entry 7). Of all the additives scanned, NaOAc
worked the best (see the Supporting Information (SI) for details). Interestingly, use of protic
conditions led to a considerable increase in the yield (Table 1, entry 8). While screening
various Brønsted-acids, AcOH was found to be the best for the transformation. The use of
TFA yielded the mixture N-allylated products 3ac and 3ac’ (Table 1, entries 8-12). Increasing
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the catalyst loading to an optimum of 10 mol% improved the transformation considerably
(Table 1, entry 9).
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Table 1. Optimization studiesa
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entry
1
catalyst
additive/oxidant
NaOAc (1 equiv.)
NaOAc (1 equiv.)
NaOAc (1 equiv.)
Cu(OAc)2 (0.2 equiv.)
Cu(OAc)2 (1 equiv.)
CsOAc (1 equiv.)
NaOAc (2 equiv.)
NaOAc (2 equiv.)
NaOAc (1 equiv.)
NaOAc (1 equiv.)
NaOAc (1 equiv.)
NaOAc (1 equiv.)
TBHP (2 equiv.)
NaOAc (1 equiv.)
acid/base
AcOH
AcOH
AcOH
K2CO3
K2CO3
K2CO3
K2CO3
AcOH
AcOH
AcOH
PivOH
TFA
(%) yield of 3a
Co(OAc)2
CoBr2
0
0
2
3
PdCl2
0
20b,c
4
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(TFA)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
5
10b,c
6
0
7
30c
8
44c
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65
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30
3ab(10)b /3ac:3ac’(20)
30c,d
-
AcOH
3b(50)e
aReaction conditions: unless otherwise mentioned all reactions performed with 1a (0.3
mmol), 2a (0.6 mmol), catalyst (0.03 mmol), 2 equiv. acid/base, O2 (1 atm) and 1.5 mL
Toluene; bGC yield; c0.015 mmol catalyst is used; dMeCN as solvent and under air; eAcOH as
solvent.
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Of the numerous solvents screened, toluene was found to be the optimal solvent for the
transformation (see the Supporting Information (SI)). The use of AcOH as the solvent led to
the exclusive formation of 3ab. As expected, a control reaction carried out in the absence of
the palladium catalyst and O2, did not yield the desired product (see the Supporting
Information (SI)).
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With the optimal reaction conditions in hand, we then explored the substrate scope for the
transformation. As it is evident from Scheme 2, the substrate scope as well as functional
group tolerance was found to be broad enough to be a practical method. The reaction worked
well with most of the anilines and allyl alcohols screened. Electronic factors were well-
tolerated on the aniline (3a-3i, Scheme 2). Further, benzylamine was also successfully
transformed into the desired product (3j, Scheme 2). The reaction was also compatible with 2o
amines to afford the desired products in moderate yields (3k-3q, Scheme 2). Interestingly,
electron-rich anilines were found to be highly reactive leading to complex mixtures under the
standard conditions. In such cases, decreasing the catalyst loading as well as the reaction
temperature, led to the formation of the desired product (3p, Scheme 2). Unfortunately this
compound was extremely susceptible to retro aza-Michael reaction, thereby reverting back to
the parent aniline during silica gel column chromatography. Interestingly, the use of indoline
led to the formation of mixture of products (3r: 3r’ 1:1 ratio) and the crude mixture was
subjected to aromatization to afford N-alkylated indole (see the Supporting Information (SI)).
Except benzyl amine, other alkyl amines were not suitable partners for this reaction.
Notably, halogen substituted anilines were easily transformed into desired products in
moderate yields, increasing the scope for further post-functionalization of the C–X bonds (3f,
3s-3x, Scheme 4). In all cases, the reaction showed excellent selectivity (N-alkylation versus
N-allylation) and majority of the substrates gave monoalkylated products. A notable exception
was also observed when crotyl alcohol failed to yield the desired product (3y, Scheme 2).
Surprisingly, the unsubstituted allyl alcohol yielded a complex mixture and the formation of
the quinoline product was observed in low yield (4a, Scheme 2). This can be explained by the
fact that the product 3-(phenylamino)propanal is highly reactive and undergoes facile
cyclization to form quinoline (4a, Scheme 2). This intriguing nature of cyclization led us to
develop a one-pot domino synthesis of quinolines as these are one of the most sought N-
heterocycles in synthetic chemistry owing to their biological prevalence and attractive
applications (Scheme 3).19
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Scheme 2: Substrate Scope for Pd-catalyzed aerobic oxidative coupling of allylic alcohols
with aminesa,b.
aUnless otherwise mentioned all reactions were performed with 1a (0.3 mmol), 2a (0.6
mmol), Pd(OAc)2 or Pd(TFA)2 (0.03 mmol), NaOAc (0.3 mmol), AcOH (0.6 mmol) and 1.5
d
mL Toluene under 1 atm O2; bAll yields are isolated yields; cPd(TFA)2 used as catalyst; 0.015
mmol Pd(OAc)2 is used and crude yield. eReaction performed on 1 mmol scale.
The aminoketones, obtained in the first step, were subjected to Lewis acid-catalyzed
electrophilic annulation in a one-pot fashion using FeCl3, to afford 4-substituted quinolines
(Scheme 3). Interestingly, these observations are completely opposite to our previous report
on ruthenium-catalyzed [3+3] annulation of anilines with allyl alcohols where we observed
the formation of 2-substituted quinolines (Scheme 1).10 In that case, we had synthesized 2-
substituted quinolines via nucleophilic attack of aniline onto the carbonyl moiety, whereas in
the present case, aromatic electrophilic substitution reaction (SEAr mechanism) of
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aminoketones is involved. As expected, naphthyl substituted anilines afforded
benzo[h]quinolines in moderate yields (4b-e, Scheme 3) and meta-substituted anilines
afforded a mixture of regioisomers (4g, 4h, Scheme 3).
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Scheme 3. One-pot synthesis of 4-substituted quinolinesa
aAll yields are isolated yields; bratio determined by 1H NMR of the crude reaction mixture.
To get more insight into the reaction pathway, control studies were carried out. Critical
information was obtained when 1-phenyl but-3-en-2-ol (2c) was reacted under standard
conditions (Scheme 4). Ketones 2ca and 2cb were detected and isolated, suggesting that the
oxidation of the allylic alcohol may be the initial step in the reaction.
Scheme 4: Control reactions
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A moderate value of kinetic isotope effect (kH/kD = 1.50) was obtained for the competitive
experiment performed with 2c and 2c’ thereby suggesting that the cleavage of the allylic C-H
bond may be involved in the rate-limiting step (Scheme 4). The use of methyl vinyl ketone
instead of but-3-en-2-ol resulted mixture of mono- and di-N-alkylated products. In addition, a
competitive experiment conducted between electronically biased anilines and but-3-en-2-ol
under optimized conditions (1k, 1o Scheme 4), resulted in the formation of corresponding
products in 3m: 3o 5:1 ratios, as shown in Scheme 4. This evidence supports the pathway
involving conjugate addition of amines onto the in situ formed enones.
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Based on the previous reports and our observations,4, 5 a plausible reaction pathway is
proposed in Scheme 5, which involves the initial oxidation of allyl alcohols to enones,
followed by aza-Michael addition to afford the desired products. Coordination of the allylic
alcohol to the catalyst to form complex B is followed by deprotonation to form Pd–alkoxide
complex C and a hydride elimination to form the enone. It is possible that Pd-catalyzed
amination with the allylic alcohol may also result in F which upon H elimination and keto-
enol tautomerization could lead to the product (Scheme 5, Pathway II). However, when the
reaction was carried out with AcOH-d4 and D2O, considerable deuterium incorporation was
observed at the position of the carbonyl group (Scheme 5).
Scheme 5: Plausible Mechanism
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A control reaction with 1-phenylbut-3-en-2-d-2-ol (2c’) with 1o did not result in any
deuterium incorporation in the corresponding product 3q (Scheme 5). These experiments
clearly indicate that the conjugate addition pathway (Scheme 5, Pathway I) was the
predominant one over the allylic amination pathway (Scheme 5, Pathway II). As the halogen
functional groups were well-tolerated in the transformation, post-functionalization of C-X
bonds can be further utilized to construct important N-heterocycles. 3-acyl indolines are
important structural motifs as they are ubiquitously present in many natural products and
several important pharmaceutically active compounds.20 The importance of indolines in
medicinal chemistry has made them relevant targets in synthetic chemistry. The palladium
catalyzed Buchwald–Hartwig carboamination is one of the most widely-utilized strategies for
the synthesis of indolines. This approach involves C-N bond coupling between an aryl halide
and an amine for the synthesis of the indoline ring through aryl amination (Scheme 6 (A)).21a
Over the years, this approach has undergone tremendous improvements for the construction of
indolines.21b However, the synthesis of indolines using sp2-sp3 C-C bond coupling is not much
explored. In this context, intramolecular -arylation of (2-bromoanilino)ketones to access
indolines and indoles would be a highly appealing approach. Palladium-catalyzed arylation
of carbonyl compounds stands out as one of the most valuable synthetic tools for the
construction of C-C bond.22 Sole and co-workers carried out an extensive study on the
chemoselective Pd-catalyzed cyclization reaction of (2-iodoanilino)carbonyl compounds and
provided insights into ketone arylation and carbonyl addition dichotomy (Scheme 6 (B)).23
Intramolecular -arylation reaction of (2-iodoanilino)-ketones using Pd(PPh3)4 as the
catalyst invariably afforded mixtures of products as shown in Scheme 6 (B). The best ratio of
 arylation product was obtained with [Pd2(dba)3] as the catalyst, KOtBu as the base in the
presence of an excess of phenol in THF and Xanthphos as the ligand (Scheme 6 (B)).23b In
this context, we initially made an attempt to synthesize various N-heterocycles through a base
mediated, palladium-catalyzed arylation of (2-bromoanilino)-ketones (5), however these
efforts were unsuccessful. The efforts led to formation of the ketone addition product along
with other side products (see the Supporting Information (SI)). Inspired by our previous work
on arylation of enones,24 we developed an approach for the synthesis of indolines utilizing
an intramolecular arylation of silylenol ethers of aminoketones (Scheme 7). The
formation of silylenol ethers followed by Pd-catalyzed arylation led to the formation of the
3-substituted indolines in a highly selective fashion (6a-6d, Scheme 7).
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Scheme 6: Palladium catalyzed synthesis of Indolines
Trace amounts of 3-substituted indoles were also observed along with the indoline products
presumably arising from the oxidation of indolines under the reaction conditions. Extended
reaction time led to the exclusive formation of 3-substituted indoles (7a, 7b, Scheme 7). The
use of Et3N, TES-OTf for the enolization of 5d and 5e led to the formation of azepines and 3-
acylindolines as the multiple enolizable positions were accessible (6d, 8a, 6e, 8b Scheme 7).
Scheme 7: Intramolecular arylation of silylenol ethers of aminoketones.a
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aAll Pd- catalyzed arylation reactions were carried out with Pd(OAc)2 (0.05 mmol), DtBPF
b
(0.05 mmol), Bu3SnF (0.42 mmol), CsF (0.42 mmol) in toluene. Trace amounts (~5%) of
azepine product (8a) was also observed
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Conclusion:
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In summary, a simple and unprecedented palladium-catalyzed oxidative coupling of allyl
alcohols with anilines to provide a rapid access to amino ketones in highly selective
fashion has been developed. The transformation is unique since it discloses a new reactivity
pattern of allylic alcohols with amines. The highlight of the present approach is the use of
readily available, bench-stable allyl alcohols and molecular oxygen as the terminal oxidant.
We have also demonstrated new utility for the amino ketones in the synthesis of various N-
heterocycles using a arylation methodology and a one-pot domino annulation. For better
understanding of the mechanism, detailed mechanistic investigations were carried out and
studies revealed that the conjugate addition pathway was the predominant one over the allylic
amination pathway.
Experimental Section:
(1) General Methods:
All commercially available compounds were used without purification. Unless otherwise
noted, all reactions were performed in oven-dried glassware. All reactions were run under
argon or nitrogen atmosphere. All solvents used in the reactions were purified before use.
Tetrahydrofuran and toluene were distilled from sodium and benzophenone, whereas dry
dichloromethane, dioxane were distilled from CaH2. 25 Petroleum ether with a boiling range
1
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of 40–60 °C was used. Melting points are uncorrected. H, and C NMR: Recorded on 400
and 500 MHz NMR Spectrometers; spectra were recorded at 295 K in CDCl3; chemical shifts
are calibrated to the residual proton and carbon resonance of the solvent: CDCl3 (1H δ 7.25;
13C δ 77.0). LC-HRMS: Recorded on a Q-ToF with electron spray ionization (ESI) or
Atmospheric pressure chemical ionization (APCI). GC-HRMS: Performed GC-QToF (with
Electron Impact (EI), 70eV) using DB-5 column. GC-LRMS: Performed GC-MS (EI 70 eV)
using DB-5 column. IR were recorded as thin films between KBr plates.
(2) General procedure for the synthesis of -aminoketones:
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(i) Synthesis of -aminoketones (A): In a Schlenk tube equipped with a stir bar, aniline (0.3
mmol) and allylic alcohol (0.6 mmol) were dissolved in dry toluene (1.5 mL). The reaction
mixture was degassed for 5-10 min followed by the addition of Pd(OAc)2 (0.03 mmol),
NaOAc (0.3 mmol), and AcOH (0.6 mmol). The tube was attached with an oxygen balloon
and the reaction mixture was vigorously stirred at 80 oC for 12-16 h during which the reaction
was found to be complete (as indicated by TLC). The reaction mixture was then cooled and
diluted with EtOAc and washed with NaHCO3 and brine. The organic extract was dried over
anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude product was
purified by a silica gel flash column chromatography to result in the desired product.
2.1. 4-(phenylamino)butan-2-one (3a):26 Yield: 65% (32 mg); Physical appearance: Yellow
oil; TLC Rf 0.3 (9:1, Petroleum ether: EtOAc); 1H NMR (400 MHz, CDCl3): δ 7.15 (t, J =
8.0, 2H), 6.69 (t, J = 7.4 Hz, 1H), 6.59 (d, J = 8.0 Hz, 2H), 4.22-3.63 (bs, 1H), 3.40 (t, J = 6.2
Hz, 2H), 2.73 (t, J = 6.2 Hz, 2H), 2.15 (s, 3H); IR (KBr, cm-1): 3394, 2918, 1709, 1601, 1504,
750; GC LR-MS: 163.1 (30%) [M]+, 145 (10%), 106 (100%).
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2.2. 1-(phenylamino)pentan-3-one (3b):26 Yield: 64% (35 mg); Physical appearance: Pale-
yellow oil; TLC Rf 0.3 (9:1, Petroleum ether: EtOAc); 1H NMR (400 MHz, CDCl3): δ 7.24 –
7.16 (m, 2H), 6.76 – 6.70 (m, 1H), 6.67 – 6.59 (m, 2H), 4.17 – 3.83 (bs, 1H), 3.45 (t, J = 6.0
Hz, 2H), 2.75 (t, J = 6.0 Hz, 2H), 2.46 (q, J = 7.2Hz, 2H), 1.08 (t, J = 7.2 Hz, 3H); IR (KBr,
cm-1): 3396, 2915, 1715, 1601, 1505, 748; ESI-LRMS: 178.1 [M+H]+.
2.3. 4-((4-nitrophenyl)amino)butan-2-one (3c): Yield: 60% (38 mg); Physical appearance:
Yellow Solid; M.p. 88-90 oC; TLC Rf 0.3 (9:1, Petroleum ether: EtOAc); 1H NMR (400 MHz,
CDCl3): δ 8.02 (d, J = 9.0 Hz, 2H), 6.4 (d, J = 9.0 Hz, 2H), 5.10 -4.90 (bs, 1H), 3.47 (t, J =
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6.0 Hz, 2H), 2.76 (t, J = 6.0 Hz, 2H), 2.16 (s, 3H); C NMR (100 MHz, CDCl3): δ 207.4,
153.0, 138.0, 126.5, 111.0, 42.1, 37.6, 30.3; IR (KBr, cm-1): 3373, 2918, 1707, 1595, 1305,
837; ESI-HRMS: Calculated for C10H13N2O3 [M+H]+ 209.0921, found 209.0908.
2.4. 4-((4-chlorophenyl)amino)butan-2-one (3d):26 Yield: 55% (32 mg); Physical
appearance: Brown solid; M.p. 54-56 oC; TLC Rf 0.3 (9:1, Petroleum ether: EtOAc); 1H NMR
(400 MHz, CDCl3): δ 7.13 (d, J = 8.5 Hz, 2H ), 6.54 (d, J = 8.5 Hz, 2H), 4.22-3.94 (bs, 1H),
3.40 (t, J = 6.0 Hz, 2H), 2.75 (t, J = 7.0 Hz, 2H), 2.19 (s, 3H); IR (KBr, cm-1): 3382, 2929,
1715, 1596, 841; GC-LRMS: 197(40%) [M]+, 180 (10%), 140 (100%).
2.5. 4-((4-fluorophenyl)amino)butan-2-one (3e):27 Yield: 54% (29 mg); Physical
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appearance: Brown oil; TLC Rf 0.3 (9:1, Petroleum ether: EtOAc); H NMR (400 MHz,
CDCl3): δ 6.93 – 6.82 (m, 2H), 6.57 – 6.48 (m, 2H), 3.92 (bs, 1H), 3.35 (t, J = 6.0 Hz, 2H),
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2.72 (t, J = 6.0 Hz, 2H), 2.14 (s, 3H); IR (KBr, cm-1): 3390, 2922, 1714, 1505, 822; GC-
LRMS: 181(50%) [M]+, 138 (10%), 124 (100%).
2.6. 4-((2-bromophenyl)amino)butan-2-one (3f): Yield: 82% (197 mg) (Reaction
performed on 1 mmol scale and excess of but-3-en-2-ol was added after 12 h); Physical
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appearance: Yellow oil; TLC Rf 0.3 (9:1, Petroleum ether: EtOAc); H NMR (400 MHz,
CDCl3): δ 7.43 (dd, J = 8.0, 1.4 Hz, 1H), 7.24 – 7.15 (m, 1H), 6.62 (d, J = 8.0 Hz, 1H), 6.60–
6.55 (m, 1H), 4.72- 4.43 (bs, 1H), 3.48 (t, J = 6.4 Hz, 2H), 2.76 (td, J = 6.4, 1.5 Hz, 2H), 2.17
(d, J = 1.5 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 207.4, 144.6, 132.6, 128.5, 118.0, 111.2,
110.1, 42.5, 38.3, 30.4; IR (KBr, cm-1): 3394, 2922, 1712, 1594, 740; ESI-HRMS:
Calculated for C10H12BrNO [M+Na]+ 263.9994 and 265.9974, found 263.9990 and 265.9980.
2.7. 4-((2-fluorophenyl)amino)butan-2-one (3g): Yield: 78% (42 mg); Physical appearance:
Yellow oil; TLC Rf 0.3 (9:1, Petroleum ether: EtOAc); 1H NMR (400 MHz, CDCl3): δ 7.03 –
6.88 (m, 2H), 6.73 – 6.65 (m, 1H), 6.65 – 6.57 (m, 1H), 4.34 – 4.04 (bs, 1H), 3.42 (t, J = 6.4
Hz, 2H), 2.74 (t, J = 6.4 Hz, 2H), 2.15 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 207.5, 151.7
(J = 234.8 Hz), 136.2 (11.2 Hz), 124.6 (J = 3.4 Hz), 116.9 (J = 6.8 Hz), 114.6 (J = 18.6 Hz),
112.1 (J = 2.3 Hz), 42.7, 38.0, 30.3; 19F NMR (471 MHz, CDCl3): δ -136.1; IR (KBr, cm-1):
3404, 2922, 1712, 1620, 744; ESI-HRMS: Calculated for C10H13FNO [M+H]+ 182.0976,
found 182.0967.
2.8. Methyl 2-((3-oxobutyl)amino)benzoate (3h): Yield: 63% (42 mg); Physical
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appearance: Yellow oil; TLC Rf 0.3 (9:1, Petroleum ether: EtOAc); H NMR (500 MHz,
CDCl3): δ 7.92 (dd, J = 8.0, 1.7 Hz, 1H), 7.82 – 7.73 (bs, 1H), 7.41 – 7.36 (m, 1H), 6.74 –
6.69 (m, 1H), 6.65 – 6.59 (m, 1H), 3.87 (s, 3H), 3.53 (q, J = 6.8 Hz, 2H), 2.83 (t, J = 6.8 Hz,
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2H), 2.22 (s, 3H); C NMR (126 MHz, CDCl3): δ 207.0, 169.0, 150.7, 134.6, 131.8, 114.8,
111.0, 110.3, 51.5, 42.9, 37.4, 30.4; IR (KBr, cm-1): 3385, 2900, 1716, 1684, 1280, 767; ESI-
HRMS: Calculated for C12H15NO3Na [M+Na]+ 244.0944, found 244.0936.
2.9. 1-((3-fluorophenyl)amino)heptan-3-one (3i): Yield: 65% (44 mg); Physical
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appearance: Reddish-oil; TLC Rf 0.3 (9:1, Petroleum ether: EtOAc); H NMR (400 MHz,
CDCl3): δ 7.10 – 7.01 (m, 1H), 6.40 – 6.29 (m, 2H), 6.29 – 6.23 (m, 1H), 4.21-4.06 (bs, 1H),
3.37 (t, J = 6.0 Hz, 2H), 2.68 (t, J = 6.0 Hz, 2H), 2.39 (t, J = 7.4 Hz, 2H), 1.59 – 1.49 (m, 2H),
1.35 – 1.22 (m, 2H), 0.88 (t, J = 7.4 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 210.4, 165.4,
164.1 (J = 242.6 Hz), 149.4 (J = 10.6 Hz), 130.3 (d, J = 10.4 Hz), 108.8 (J = 2.2 Hz), 99.5
(26.5 Hz), 42.9, 41.4, 38.3, 25.8, 22.3, 13.8;19F NMR (470 MHz, CDCl3): δ -112.8; IR (KBr,
cm-1): 3393, 2955, 1703, 1622, 756; ESI-HRMS: Calculated for C13H19NFO [M+H]+
224.1445, found 224.1435.
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2.10. 1-((4-nitrobenzyl)amino)propan-2-one (3j): Yield: 68% (46 mg); Physical
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appearance: Reddish oil; TLC Rf 0.3 (9:1, Petroleum ether: EtOAc); H NMR (400 MHz,
CDCl3): δ 8.18 (d, J = 8.2 Hz, 2H), 7.50 (d, J = 8.2 Hz, 2H), 5.38 – 4.01 (bs, 1H), 2.77 (t, J =
6.8 Hz, 2H), 2.68 (t, J = 6.8 Hz, 2H), 2.22 (s, 2H), 2.18 (s, 3H); 13C NMR (100 MHz,
CDCl3): δ 207.6, 147.2, 146.3, 129.5, 123.6, 61.5, 52.0, 41.9, 41.6, 30.1; IR (KBr, cm-1):
2922, 1712, 1519, 1265, 737; ESI-HRMS: Calculated for C12H17N2O3 [M+H]+ 237.1234,
found 237.1230.
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2.11. 1-(methyl(phenyl)amino)heptan-3-one (3k): Yield: 80% (52 mg); Physical
appearance: Pale-yellow oil; TLC Rf 0.3 (9:1, Petroleum ether: EtOAc); 1H NMR (400 MHz,
CDCl3): δ 7.29 – 7.18 (m, 2H), 6.75 – 6.64 (m, 3H), 3.64 (t, J = 7.0 Hz, 2H), 2.90 (s, 3H),
2.65 (t, J = 7.0 Hz, 2H), 2.38 (t, J = 7.4 Hz, 2H), 1.62 – 1.43 (m, 2H), 1.34 – 1.19 (m, 2H),
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0.87 (t, J = 7.4 Hz, 3H); C NMR (100 MHz, CDCl3): δ 210.5, 148.7, 129.3, 116.6, 112.4,
47.5, 43.3, 39.3, 38.5, 25.8, 22.3, 13.8; IR (KBr, cm-1): 2971, 1710, 1600, 1506, 750; ESI-
HRMS: Calculated for C14H22NO [M+H]+ 220.1696, found 220.1711.
2.12. 1-(methyl(phenyl)amino)pentan-3-one (3l): Yield: 78% (44 mg); Physical
appearance: Pale-yellow oil; TLC Rf 0.3 (9:1, Petroleum ether: EtOAc); 1H NMR (400 MHz,
CDCl3): δ 7.29 – 7.20 (m, 2H), 6.80 – 6.66 (m, 3H), 3.65 (t, J = 7.0 Hz, 2H), 2.92 (s, 3H),
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2.67 (t, J = 7.0 Hz, 2H), 2.42 (q, J = 7.2 Hz, 2H), 1.06 (t, J = 7.2 Hz, 3H); C NMR (100
MHz, CDCl3): δ 210.7, 148.7, 129.3, 116.6, 112.5, 47.6, 39.0, 38.5, 36.7, 7.7; IR (KBr, cm-1):
2975, 1712, 1604, 1510, 750; ESI-HRMS: Calculated for C12H18NO [M+H]+ 192.1383,
found 192.1371.
2.13. 4-(methyl(phenyl)amino)butan-2-one (3m): Yield: 76% (40 mg); Physical
appearance: Pale-yellow oil; TLC Rf 0.3 (9:1, Petroleum ether: EtOAc); 1H NMR (400 MHz,
CDCl3): δ 7.28 – 7.19 (m, 2H), 6.77 – 6.63 (m, 3H), 3.63 (d, J = 6.8 Hz, 2H), 2.91 (s, 3H),
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2.69(t, J = 6.8 Hz, 2H), 2.14 (s, 3H); C NMR (100 MHz, CDCl3): δ 208.0, 148.7, 129.3,
116.7, 112.5, 47.3, 40.3, 38.5, 30.6; IR (KBr, cm-1): 2921, 1714, 1609, 1505, 751; ESI-
HRMS: C11H16NO [M+H]+ 178.1226, found 178.1227.
2.14. 3-(methyl(phenyl)amino)-1-phenylpropan-1-one (3n): Yield: 70% (50 mg); Physical
appearance: Pale-yellow oil; TLC Rf 0.3 (9:1, Petroleum ether: EtOAc); 1H NMR (400 MHz,
CDCl3): δ 7.99 – 7.94 (m, 2H), 7.63 – 7.55 (m, 1H), 7.52 – 7.45 (m, 2H), 7.33 – 7.25 (m, 2H),
6.83 – 6.72 (m, 3H), 3.88 (d, J = 2.0 Hz, 2H), 3.27 (d, J = 2.0 Hz, 2H), 3.01 (s, 3H); 13C
NMR (100 MHz, CDCl3): δ 199.5, 148.6, 136.9, 133.2, 129.4, 128.7, 128.1, 116.6, 112.4,
48.0, 38.6, 35.2; IR (KBr, cm-1): 2923, 1690, 1598, 1445, 1204, 748; ESI-HRMS: Calculated
for C16H18NO [M+H]+ 240.1383, found 240.1379.
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2.15. 4-(methyl(4-nitrophenyl)amino)butan-2-one (3o): Yield: 70% (47 mg); Physical
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appearance: Yellow Solid; M.p. 93-95 C; TLC Rf 0.3 (9:1, Petroleum ether: EtOAc); 1H
NMR (500 MHz, CDCl3): δ 8.15 – 8.10 (m, 2H), 6.81 – 6.38 (m, 2H), 3.76 (t, J = 6.8 Hz,
2H), 3.11 (s, 3H), 2.80 (t, J = 6.8 Hz, 2H), 2.21 (s, 3H); 13C NMR (126 MHz, CDCl3): δ
206.6, 152.9, 137.2, 126.3, 110.3, 46.9, 40.5, 39.0, 30.5; IR (KBr, cm-1): 2920, 1705, 1510,
1345, 737; ESI-HRMS: Calculated for C11H14N2O3Na [M+Na]+ 245.0897, found 245.0917.
2.16. 4-((4-methoxyphenyl)(methyl)amino)butan-2-one (3p): Yield: 65% (40 mg);
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Physical appearance: Pale-yellow oil; TLC Rf 0.3 (9:1, Petroleum ether: EtOAc); H NMR
(400 MHz, CDCl3): δ 6.84 (d, J = 8.8 Hz, 2H), 6.73 (d, J = 8.8 Hz, 2H), 3.76 (s, 3H), 3.55 (d,
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J = 6.8 Hz, 2H), 2.84 (s, 3H), 2.66 (t, J = 6.8 Hz, 2H), 2.14 (s, 3H); C NMR:(100 MHz,
CDCl3): δ 208.1, 152.1, 143.7, 115.2, 114.8, 55.7, 48.6, 40.2, 39.3, 30.57; IR (KBr, cm-1):
2926, 1706, 1243, 1033, 814; ESI-HRMS: Calculated for C12H18NO2, [M+H]+ 208.1332,
found 208.1303.
2.17. 4-(methyl(4-nitrophenyl)amino)-1-phenylbutan-2-one (3q): Yield: 50% (45 mg);
o
Physical appearance: Yellow Solid; M.p. 57-59 C; TLC Rf 0.3 (9:1, Petroleum ether:
EtOAc); 1H NMR (400 MHz, CDCl3): δ 8.12 – 7.98 (m, 2H), 7.39 – 7.29 (m, 3H), 7.25 –
7.15 (m, 2H), 6.50 (d, J = 9.4 Hz, 2H), 3.77 – 3.65 (m, 4H), 3.00 (d, J = 1.0 Hz, 3H), 2.79 (t,
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J = 6.8 Hz, 2H); C NMR (100 MHz, CDCl3): δ 206.5, 152.8, 137.1, 133.4, 129.4, 129.0,
127.4, 126.2, 110.2, 50.9, 47.3, 38.9, 38.5; IR (KBr, cm-1): 2918, 1715, 1592, 1305, 823, 744;
ESI-HRMS: Calculated for C17H19N2O3 [M+H]+ 299.1390, found 299.1379.
2.18. 1-(1H-indol-1-yl)pentan-3-one (3r’):Yield: 60% (36 mg); Physical appearance: Brown
solid; M.p. 56-58; TLC Rf 0.3 (9:1, Petroleum ether: EtOAc); 1H NMR (400 MHz, CDCl3): δ
7.69 (m, 1H), 7.40 – 7.33 (t, 1H), 7.28 – 7.22 (m, 1H), 7.17 – 7.10 (t, 2H), 6.50 (dd, J = 3.2,
0.8 Hz, 1H), 4.47 (t, J = 6.8 Hz, 2H), 2.94 (t, J = 6.8 Hz, 2H), 2.37 (d, J = 7.2 Hz, 2H), 1.04
(t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 209.2, 135.6, 128.7, 128.2, 121.6, 121.1,
119.4, 109.1, 101.4, 42.2, 40.8, 36.6, 7.5; IR (KBr, cm-1): 2924, 1710, 1605, 1340, 840; ESI-
HRMS: Calculated for C13H15NONa [M+Na]+ 224.1046, found 224.1042.
2.19. 4-((2-bromo-4-methylphenyl)amino)butan-2-one (3s): Yield: 84% (64 mg); Physical
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appearance: Yellow oil; TLC Rf 0.3 (9:1, Petroleum ether: EtOAc); H NMR (400 MHz,
CDCl3): δ 7.28 (s, 1H), 7.01 (d, J = 8.2 Hz, 1H), 6.59 (d, J = 8.2 Hz, 1H), 4.41 (bs, 1H), 3.46
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(t, J = 4.6 Hz, 2H), 2.79 (t, J = 6.4 Hz, 2H), 2.24 (s, 3H), 2.20 (s, 3H); C NMR (100 MHz,
CDCl3): δ 207.5, 142.3, 132.9, 129.0, 127.6, 111.3, 110.1, 42.6, 38.6, 30.4, 20.0; IR (KBr,
cm-1): 3396, 2921, 1710, 1598, 760; ESI-HRMS: Calculated for C11H14BrNONa [M+Na]+
278.0151 and 280.0131, found 278.0126 and 280.0108.
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(ii) General procedure for the synthesis of -aminoketones (B):
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In a Schlenk tube equipped with a stir bar, 1-phenylprop-2-en-1-ol (0.6 mmol) was dissolved
in dry toluene (1.5 mL). The reaction mixture was degassed for 5-10 min followed by the
addition of Pd(OAc)2 (0.03 mmol), NaOAc (0.3 mmol), and AcOH (0.6 mmol). The tube was
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attached with an oxygen balloon and the reaction mixture was vigorously stirred at 80 C for
4-6 h. After cooling to the room temperature, aniline (0.3 mmol) was added and the resulting
reaction mixture was allowed to stir at 60 oC for 12 – 18 h. This was then diluted with EtOAc
and washed with NaHCO3 and brine. The organic extract was dried over anhydrous Na2SO4,
filtered and concentrated under reduced pressure. The crude product was purified by silica gel
flash column chromatography to result in the desired product.
2.20. 3-((2-bromo-4-methylphenyl)amino)-1-(3-methoxyphenyl)propan-1-one (3t): Yield:
55% (57 mg); Physical appearance: Yellow solid; M.p. 64-66 oC; TLC Rf 0.3 (9:1, Petroleum
ether: EtOAc); 1H NMR (400 MHz, CDCl3): δ 7.55 (d, J = 7.6 Hz, 1H), 7.51 (s, 1H), 7.39 (t,
J = 8.0 Hz, 1H), 7.28 (s, 1H), 7.13 (t, J = 8.0 Hz, 1H), 7.02 (d, J = 8.2 Hz, 1H), 6.66 (d, J =
8.2 Hz, 1H), 4.55 (bs, 1H), 3.87 (s, 3H), 3.65 (t, J = 6.4 Hz, 2H), 3.31 (t, J = 6.4 Hz, 2H), 2.24
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(s, 3H); C NMR (100 MHz, CDCl3): δ 198.7, 158.9, 142.4, 138.1, 133.0, 129.7, 129.0,
127.6, 120.7, 119.9, 112.2, 111.4, 110.1, 55.5, 39.1, 37.9, 20.0; IR (KBr, cm-1): 2910, 1690,
1604, 1249, 749; ESI-HRMS: Calculated for C17H19BrNO2 [M+H]+ 348.0594 and 350.0573,
found 348.0570 and 350.0553.
2.21. 3-((2-bromo-4-methylphenyl)amino)-1-phenylpropan-1-one (3u): Yield: 51% (48
1
mg); Physical appearance: Pale-yellow oil; TLC Rf 0.3 (9:1, Petroleum ether: EtOAc); H
NMR (400 MHz, CDCl3): δ 7.99 (d, J = 7.8 Hz, 2H), 7.64 – 7.55 (m, 1H), 7.49 (t, J = 7.4 Hz,
2H), 7.28 (s, 1H), 7.03 (d, J = 8.0 Hz, 1H), 6.66 (d, J = 8.0 Hz, 1H), 3.67 (t, J = 6.4 Hz, 2H),
3.33 (t, J = 6.4 Hz, 2H), 2.22 (s, 3H), 4.73-4.40 (bs, 1H); 13C NMR (100 MHz, CDCl3): δ
198.9, 142.4, 136.8, 133.4, 133.0, 129.0, 128.7, 128.1, 127.6, 111.4, 110.1, 39.0, 37.7, 20.0;
IR (KBr, cm-1): 2918, 1734, 1610, 1489, 1267, 739; ESI-HRMS: Calculated for C16H17BrNO
[M+H]+ 318.0488 and 320.0468, found 318.0464 and 320.0447.
2.22. 3-((2-bromophenyl)amino)-1-(3-methoxyphenyl)propan-1-one (3v): Yield: 49% (49
1
mg); Physical appearance: Yellow oil; TLC Rf 0.3 (9:1, Petroleum ether: EtOAc); H NMR
(400 MHz, CDCl3): δ 7.55 (d, J = 7.6 Hz, 1H), 7.52 (s, 1H), 7.44 (d, J = 8.0 Hz, 1H), 7.39 (t,
J = 7.8 Hz, 1H), 7.22 (t, J = 7.8 Hz, 1H), 7.14 (d, J = 8.2 Hz, 1H), 6.74 (d, J = 8.2 Hz, 1H),
6.60 (t, J = 7.8 Hz, 1H), 4.77 (bs, 1H), 3.87 (s, 3H), 3.68 (t, J = 6.4 Hz, 2H), 3.32 (t, J = 6.4
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Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 198.6, 159.9, 144.6, 138.0, 132.6, 129.7, 128.5,
120.7, 119.9, 118.0, 112.3, 111.2, 110.1, 55.5, 38.8, 37.8; IR (KBr, cm-1): 2909, 1680, 1598,
1256, 739; ESI-HRMS: Calculated for C16H16NBrO2Na [M+Na]+ 356.0257 and 358.0236,
found 356.0275 and 358.0256.
2.23. 3-((2-bromo-4-methylphenyl)amino)-1-phenylpropan-1-one (3w):28 Yield: 48% (43
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mg); Physical appearance: Pale-yellow oil; TLC Rf 0.3 (9:1, Petroleum ether: EtOAc); H
NMR (400 MHz, CDCl3): δ 7.95 (d, J = 7.6 Hz, 2H), 7.56 (t, J = 7.2 Hz, 1H), 7.49 – 7.37 (m,
3H), 7.19 (t, J = 7.6 Hz, 1H), 6.71 (d, J = 8.0 Hz, 1H), 6.57 (t, J = 7.6 Hz, 1H), 4.71 (s, 1H),
3.71-3.56 (m, 2H), 3.29 (t, J = 6.4 Hz, 2H); IR (KBr, cm-1): 2911, 1716, 1601, 1400, 758;
ESI-LRMS: 304.2 [M+H]+.
2.24. 4-((2-bromophenyl)amino)-1-phenylbutan-2-one (3x): Yield: 40% (39 mg); Physical
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appearance: Yellow oil; TLC Rf 0.3 (9:1, Petroleum ether: EtOAc); HNMR (400 MHz,
CDCl3): δ 7.46 (d, J = 6.6 Hz, 1H), 7.42 – 7.29 (m, 3H), 7.27 – 7.14 (m, 3H), 6.70-6.53 (m,
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2H), 4.58 (s, 1H), 3.74 (s, 2H), 3.47 (t, J = 6.0 Hz, 2H), 2.81 (t, J = 6.0 Hz, 2H); C NMR
(100 MHz, CDCl3): δ 207.2, 144.5, 133.9, 132.6, 129.5, 128.9, 128.6, 127.2, 118.0, 111.2,
110.1, 50.6, 40.8, 38.4; IR (KBr, cm-1): 2923, 1712, 1594, 1452, 1079, 741, 698; ESI-
HRMS: Calculated for C16H16NBrONa [M+Na]+ 340.0307 and 342.0287, found 340.0280
and 342.0288.
2.25 4,4'-(phenylazanediyl)bis(butan-2-one) (3aa):12c Yield: 28% (19 mg); Physical
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appearance: Yellow oil; TLC Rf 0.2 (9:1, Petroleum ether: EtOAc); HNMR (400 MHz,
CDCl3): δ 7.24 – 7.18 (m, 2H), 6.71 (t, J = 7.2 Hz, 1H), 6.64 (d, J = 8.2 Hz, 2H), 3.57 (t, J =
7.0 Hz, 4H), 2.70 (t, J = 7.0 Hz, 4H), 2.14 (s, 6H).
(3) General procedure for the one-pot synthesis of 4-substituted quinolines:
In a Schlenk tube equipped with a stir bar, aniline (0.3 mmol) and allylic alcohol (0.6 mmol)
were dissolved dry toluene (1.5 mL). The reaction mixture was degassed for 5-10 min
followed by the addition of Pd(OAc)2 (0.03 mmol), NaOAc (0.3 mmol), and AcOH (0.6
mmol). The tube was attached with an oxygen balloon and the mixture was vigorously stirred
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at 80 C for 6-12 h. After completion of the reaction, FeCl3.6H2O (0.3 mmol, 81 mg in 0.5
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mL EtOH) was added and the resulting allowed to stir at 60 C for 12 h. Upon cooling to
room temperature, the reaction mixture was diluted with EtOAc and washed with 1 N NaOH
and brine. The organic extract was dried over anhydrous Na2SO4, filtered and concentrated
under reduced pressure. The crude product was purified by a silica gel flash column
chromatography to result in the desired product.
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3.1. 4-methylquinoline (4b):Yield: 42% (18 mg); Physical appearance: yellowish oil; TLC Rf
0.40 (9:1, Petroleum ether: EtOAc); 1H NMR (400 MHz, CDCl3): δ 8.76 (d, J = 4.2 Hz, 1H),
8.09 (d, J = 8.4 Hz, 1H), 7.99 (d, J = 8.4 Hz, 1H), 7.74-7.65 (m,1H), 7.58-7.51(m, 1H), 7.20
(d, J = 4.2 Hz, 1H), 2.68 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 150.2, 148.0, 144.3, 130.0,
129.1, 128.3, 126.3, 123.8, 121.9, 18.6; IR (KBr cm-1): 2920, 1596, 1454, 539, 757; ESI-
HRMS: Calculated for C10H10N [M+H]+ 144.0808, found 144.0823.
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3.2. 4-methylbenzo[h]quinolone (4c):29 Yield: 47% (27 mg); Physical appearance: Brown
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oil; TLC Rf 0.40 (9:1, Petroleum ether: EtOAc); H NMR (400 MHz, CDCl3): δ 9.33 (d, J =
8.0 Hz, 1H), 8.05 (d, J = 8.0 Hz, 1H), 7.91-7.85 (m,1H), 7.77-7.59 (m, 4H), 7.37 (d, J = 8.0
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Hz, 1H), 2.83 (s ,3H); C NMR (100 MHz, CDCl3): δ 157.8, 146.0, 135.9, 133.7, 131.3,
127.9, 127.7, 127.6, 126.6, 125.2, 124.4, 124.2, 122.2, 25.4; IR (KBr cm-1): 2959, 2926,
1596, 1394, 841; GC-LRMS: 193 (100%) [M]+, 165 (15%), 143 (10%).
3.3. 4-butylbenzo[h]quinolone (4d): Yield: 45% (32 mg); Physical appearance: Pale-yellow
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oil; TLC Rf 0.40 (9:1, Petroleum ether: EtOAc); H NMR (400 MHz, CDCl3): δ 9.36 (d, J =
7.6 Hz, 1H), 8.05 (d, J = 8.2 Hz, 1H), 7.88 (d, J = 7.4 Hz ,1H), 7.78-7.58 (m,4H), 7.39 (d, J =
8.2 Hz, 1H), 3.08 (t, J = 7.8 Hz, 2H), 1.98-1.84 (m, 2H), 1.54-1.42 (m, 2H), 0.99 (t, J = 7.4
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Hz, 3H); C NMR (100 MHz, CDCl3): δ 161.7, 145.9, 135.8, 133.7, 131.5, 127.9, 127.6,
126.7, 126.6, 125.2, 124.6, 124.3, 121.6, 38.7, 31.9, 22.6, 14.1; IR (KBr cm-1): 2955, 1596,
1507, 1395, 843, 751; ESI-HRMS: Calculated for C17H18N [M+H]+ 236.1434, found
236.1425.
3.4. 4-propylbenzo[h]quinolone (4e): Yield: 44% (43 mg); Physical appearance: Pale-
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yellow oil; TLC Rf 0.40 (9:1, Petroleum ether: EtOAc); H NMR (400 MHz, CDCl3): δ 9.35
(d, J = 8.0 Hz, 1H), 8.05 (d, J = 8.2 Hz, 1H), 7.88 (d, J = 8.0 Hz, 1H), 7.80-7.60 (m, 4H), 7.37
(d, J = 8.2 Hz, 1H), 3.04 (t, J = 7.6 Hz, 2H), 2.01-1.88 (m, 2H), 1.06 (t, J = 7.4 Hz, 3H); 13C
NMR (100 MHz, CDCl3): δ 161.5, 146.0, 135.8, 133.7, 131.6, 127.8, 127.6, 126.7, 126.6,
125.2, 124.5, 124.3, 121.7, 41.1, 23.0, 14.0; IR (KBr cm-1): 2959, 2926, 1596, 1505, 1394,
841, 752; ESI-HRMS: Calculated for C16H16N [M+H]+ 222.1277, found 222.1302.
3.5. 4-pentylbenzo[h]quinolone (4f): Yield: 37% (29 mg); Physical appearance: Yellow oil;
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TLC Rf 0.40 (9:1, Petroleum ether: EtOAc); H NMR (400 MHz, CDCl3): δ 9.36 (d, J = 8.0
Hz, 1H), 8.05 (d, J = 8.2 Hz, 1H), 7.89 (d, J = 8.0 Hz, 1H), 7.80-7.59 (m, 4H), 7.38 (d, J = 8.4
Hz, 1H), 3.07 (t, J = 8.0 Hz, 2H), 1.47-1.37 (m, 4H), 2.0-1.86 (m,2H), 0.92 (t, J = 7.0, 3H);
13C NMR (100 MHz, CDCl3): δ 161.7, 149.4, 135.8, 133.7, 131.5, 127.8, 127.6, 126.7, 126.6,
125.2, 125.5, 124.3, 121.6, 39.1, 31.7, 29.4, 22.6, 14.1; IR (KBr cm-1): 2954, 2925, 1596,
1450, 1209, 842; ESI-HRMS: Calculated for C18H20N [M+H]+ 250.1590, found 250.1598.
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3.6. 4,7-dimethylquinoline and 4,5-dimethylquinoline (4g:4g’ (3:1)): Yield: 37% (18 mg);
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Physical appearance: yellowish oil; TLC Rf 0.40 (9:1, Petroleum ether : EtOAc); H NMR
(400 MHz, CDCl3): δ 8.71 (d, J = 4.4 Hz, 1H), 7.89-7.83 (m, 2H), 7.41-734 (m,1H), 7.17-
7.14 (m, 1H), 2.67 (s, 3H), 2.55 (s, 3H), 8.66 (d, J = 4.4 Hz, 1H), 7.94 (d, J = 8.4 Hz, 1H),
7.54-7.48 (m, 1H), 7.31-7.27 (m, 1H), 7.14-7.11 (m, 1H), 2.93-2.88 (m, 6H); 13C NMR (100
MHz, CDCl3): δ 150.1, 149.4, 148.2, 144.1, 139.3, 129.5, 129.1, 128.9, 128.5, 126.3, 124.0,
123.5, 121.2, 25.6, 25.3, 21.7, 18.6; IR (KBr cm-1): 2923, 1586, 1459, 1036, 753; ESI-
HRMS: Calculated for C11H12N [M+H]+ 158.0964, found 158.0965.
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3.7. 4-butyl-7-methylquinoline and 4-butyl-5-methylquinoline (4h:4h’ (6:1)): Yield: 40%
(26 mg); Physical appearance: Brown liquid; TLC Rf 0.40 (9:1 Petroleum ether: EtOAc 5:1);
1H NMR (400 MHz, CDCl3): δ 8.00 (d. J = 8.4 Hz, 1H), 7.80 (s, 1H), 7.65 (d, J = 8.4 Hz,
1H), 7.34-7.25 (m,1H), 7.21 (d, J = 8.2 Hz, 1H), 2.94 (t, J = 8.0 Hz, 2H), 2.53 (s, 3H), 1.85-
1.70 (m, 2H), 1.48-1.34 (m, 2H), 0.94 (t, J = 7.4 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ
163.1, 148.2, 139.5, 135.8, 128.0, 127.8, 127.1, 124.7, 120.5, 39.1, 32.2, 22.7, 21.9, 14.0; IR
(KBr cm-1): 2914, 1624, 1549, 1405, 1201, 810; ESI-HRMS: Calculated for C14H18N
[M+H]+ 200.1434, found 200.1433.
(4) General procedure for the N-Benzylation of -aminoketones:23a To a solution of 4-((2-
bromophenyl)amino)butan-2-one(0.12 g, 0.5 mmol) in CH3CN (3 mL), benzyl bromide (0.3
mL, 2.5 mmol) and K2CO3 (0.28 g, 2.0 mmol) were added and the mixture was vigorously
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stirred at 40 C for 36 -48 h. Upon completion, the reaction mixture was diluted with EtOAc
and washed with brine. The organic extract was dried over anhydrous Na2SO4, filtered and
concentrated under reduced pressure. The crude product was purified by silica gel flash
column chromatography to result in the desired product.
4.1. 3-(benzyl(2-bromophenyl)amino)-1-phenylpropan-1-one (5a): Yield: 65% (191 mg);
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Physical appearance: Pale-yellow oil; TLC Rf 0.3 (19:1, Petroleum ether: EtOAc); H NMR
(400 MHz, CDCl3): δ 7.83 (d, J = 8.0 Hz, 2H), 7.63 (d, J = 8.0 Hz, 1H), 7.54 (t, J = 7.4 Hz,
1H), 7.45 – 7.38 (m, 4H), 7.36 – 7.22 (m, 4H), 7.16 (d, J = 8.0 Hz, 1H), 6.98 (t, J = 7.6 Hz,
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1H), 4.26 (s, 2H), 3.51 (d, J = 7.4 Hz, 2H), 3.12 (t, J = 7.4 Hz, 2H); C NMR (100 MHz,
CDCl3): δ 199.2, 148.7, 138.1, 136.8, 134.0, 133.0, 128.6, 128.5, 128.3, 128.0, 127.9, 127.2,
125.3, 124.5, 122.4, 59.0, 47.4, 36.6; IR (KBr cm-1): 2924, 1701, 1621, 1410, 762; ESI-
HRMS: Calculated for C22H20BrNONa [M+Na]+ 416.0620 and 418.0600, found 416.0642
and 418.0615.
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4.2. 3-(benzyl(2-bromophenyl)amino)-1-(3-methoxyphenyl)propan-1-one (5b): Yield:
60% (190 mg); Physical appearance: Yellow oil; TLC Rf 0.3 (19:1, Petroleum ether: EtOAc);
1H NMR (400 MHz, CDCl3): δ 7.63 (d, J = 8.0 Hz, 1H), 7.45 – 7.36 (m, 4H), 7.35 – 7.23 (m,
5H), 7.16 (d, J = 8.0 Hz, 1H), 7.09 (d, J = 8.4 Hz, 1H), 6.97 (t, J = 7.6 Hz, 1H), 4.26 (s, 2H),
3.02 (s, 3H), 3.51 (t, J = 7.4 Hz, 2H), 3.11 (t, J = 7.4 Hz, 2H); 13C NMR (100 MHz, CDCl3):
δ 199.0, 159.8, 148.7, 138.2, 138.1, 134.0, 129.5, 128.6, 128.3, 127.9, 127.2, 125.3, 124.5,
122.3, 120.7, 119.4, 112.2, 59.0, 55.4, 47.6, 36.7; IR (KBr cm-1): 2914, 1686, 1591, 1471,
1254, 755; ESI-HRMS: Calculated for C23H23BrNO2, [M+H]+ 424.0907 and 426.0886, found
424.0903 and 426.0887.
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4.3. 3-(benzyl(2-bromo-4-methylphenyl)amino)-1-(3-methoxyphenyl)propan-1-one (5c):
Yield: 58% (190 mg); Physical appearance: Yellow oil; TLC Rf 0.3 (19:1, Petroleum ether:
EtOAc); 1H NMR (400 MHz, CDCl3): δ 7.48 – 7.36 (m, 5H), 7.32 (t, J = 7.6 Hz, 3H), 7.29 –
7.21 (m, 1H), 7.12 – 7.02 (m, 3H), 4.21 (s, 2H), 3.84 (s, 3H), 3.47 (t, J = 7.4 Hz, 2H), 3.09 (t,
J = 7.4 Hz, 2H), 2.31 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 199.1, 159.7, 146.0, 138.3,
138.2, 135.4, 134.3, 129.5, 128.7, 128.6, 128.2, 127.1, 124.2, 122.3, 120.7, 119.5, 112.2,
59.3, 55.4, 47.4, 36.8, 20.4; IR (KBr, cm-1): 2921, 1685, 1491, 1259, 1037, 746; ESI-HRMS:
Calculated for C24H25BrNO2 [M+H]+ 438.1063 and 440.1043, found 438.1090 and 440.1073.
4.4. 4-(benzyl(2-bromophenyl)amino)butan-2-one (5d): Yield: 80% (198 mg); Physical
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appearance: Yellow oil; TLC Rf 0.3 (19:1, Petroleum ether: EtOAc); H NMR (400 MHz,
CDCl3): δ 7.63 (dd, J = 8.0, 1.4 Hz, 1H), 7.40 – 7.35 (m, 2H), 7.35 – 7.29 (m, 2H), 7.29 –
7.22 (m, 2H), 7.08 (dd, J = 8.0, 1.6 Hz, 1H), 6.90 (ddd, J = 8.0, 7.4, 1.6 Hz, 1H), 4.18 (s, 2H),
3.32 (t, J = 7.2 Hz, 2H), 2.56 (t, J = 7.2 Hz, 2H), 2.06 (s, 3H); 13C NMR (100 MHz, CDCl3):
δ 207.8, 148.5, 137.9, 134.0, 128.7, 128.2, 127.9, 127.2, 125.4, 124.5, 122.4, 59.0, 46.6, 41.5,
30.2; IR (KBr, cm-1): 2914, 1712, 1357, 1024, 752; ESI-HRMS: Calculated for
C17H19BrNO, [M+H]+ 332.0645 and 334.0624, found 332.0638 and 334.0619.
4.5. 4-(benzyl(2-bromo-4-methylphenyl)amino)butan-2-one(5e): Yield: 76% (197 mg);
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Physical appearance: Yellow oil; TLC Rf 0.3 (19:1, Petroleum ether: EtOAc); H NMR (400
MHz, CDCl3): δ 7.42 (s, 1H), 7.34 (d, J = 7.2 Hz, 2H), 7.30 – 7.18 (m, 3H), 7.00 (d, J = 8.2
Hz, 1H), 6.93 (d, J = 8.2 Hz, 1H), 4.09 (s, 2H), 3.24 (t, J = 7.2 Hz, 2H), 2.50 (t, J = 7.2 Hz,
2H), 2.27 (s, 3H), 2.01 (s, 3H); 13C NMR (126 MHz, CDCl3): δ 208.0, 145.8, 138.1, 135.5,
134.3, 128.8, 128.6, 128.2, 127.2, 124.3, 122.4, 59.4, 46.9, 41.6, 30.2, 20.5; IR (KBr, cm-1):
2916, 1708, 1624, 1451, 748; ESI-HRMS: Calculated for C18H20BrNONa [M+Na]+ 368.0620
and 370.0600, found 368.0645 and 370.0630.
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(5) General procedure for -arylation of -aminoketones: The arylation of TES enol
ethers of various -aminoketones was performed according to procedure in our previous
report.18
(a) Step I: Synthesis of TES-enol ether of -aminoketones: TES-Cl (0.05 mL, 0.3 mmol)
was added to a stirring solution of -aminoketones (0.3 mmol) and DBU (0.09 mL, 0.6
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mmol) in dry CH2Cl2 (5 mL) at room temperature. The reaction mixture was heated to 40 C
and allowed to stir at that temperature for 18 h. After completion of the reaction, the solution
was poured into saturated aqueous NaHCO3 and extracted with DCM. The organic layer was
dried (anhydrous Na2SO4), filtered and concentrated. The residue was immediately used for
the next step.
(b) Step II: -arylation of TES-enol ether of -aminoketones: The -arylation of TES
enol ethers of various -aminoketones was performed according to our previous report.18
5.1. (1-benzylindolin-3-yl)(phenyl)methanone (6a): Yield: 58% (46 mg); Physical
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appearance: Yellow oil; TLC Rf 0.3 (19:1, Petroleum ether: EtOAc); H NMR (400 MHz,
CDCl3): δ 8.14 – 8.02 (m, 2H), 7.69 – 7.62 (m, 1H), 7.60 – 7.51 (m, 2H), 7.47 – 7.35 (m, 4H),
7.33 – 7.30 (m, 1H), 7.11 (d, J = 7.8 Hz, 1H), 6.90 (d, J = 7.4 Hz, 1H), 6.64 – 6.55 (m, 2H),
5.13 (t, J = 8.8 Hz, 1H), 4.49 (d, J = 15.2 Hz, 1H), 4.29 (d, J = 15.2 Hz, 1H), 3.97 – 3.87 (m,
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1H), 3.67 (d, J = 9.4 Hz, 1H); C NMR (100 MHz, CDCl3): δ 197.5, 152.1, 138.0, 136.9,
133.4, 129.1, 128.8, 128.7, 128.6, 127.8, 127.2, 125.0, 117.8, 117.6, 107.4, 55.2, 53.1, 48.3;
IR (KBr, cm-1): 2914, 1693, 1620, 1520, 1375, 871, 748; ESI-HRMS: Calculated for
C22H19NONa [M+Na]+ 336.1359, found 336.1382.
5.2. (1-benzylindolin-3-yl)(3-methoxyphenyl)methanone (6b): Yield: 62% (53 mg);
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Physical appearance: Yellow oil; TLC Rf 0.3 (19:1, Petroleum ether: EtOAc); H NMR (400
MHz, CDCl3): δ 7.62 (d, J = 7.4 Hz, 1H), 7.56 (s, 1H), 7.48 – 7.22 (m, 6H), 7.16 (d, J = 8.2
Hz, 1H), 7.07 (d, J = 7.6 Hz, 1H), 6.88 (d, J = 7.4 Hz, 1H), 6.61 – 6.50 (m, 2H), 5.07 (t, J =
8.6 Hz, 1H), 4.45 (d, J = 15.2 Hz, 1H), 4.26 (d, J = 15.2 Hz, 1H), 3.92 – 3.78 (m, 4H), 3.62 (t,
J = 9.4 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ 197.3, 160.0, 152.1, 138.3, 138.0, 129.8,
129.0, 128.7, 128.6, 127.8, 127.2, 125.0, 121.7, 120.0, 117.6, 113.2, 107.4, 55.5, 55.3, 53.1,
48.5; IR (KBr, cm-1): 2923, 1653, 1614, 1375, 1173, 1033; ESI-HRMS: Calculated for
C23H21NO2Na [M+Na]+ 366.1465, found 366.1468.
5.3. (1-benzyl-5-methylindolin-3-yl)(3-methoxyphenyl)methanone (6c): Yield: 56% (50
o
mg); Physical appearance: Off-white solid, M.p. 98-100 C; TLC Rf 0.3 (19:1, Petroleum
ether: EtOAc); 1H NMR (400 MHz, CDCl3): δ 7.66 (d, J = 7.6 Hz, 1H), 7.60 (s, 1H), 7.51 –
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7.41 (m, 3H), 7.37 (t, J = 7.4 Hz, 2H), 7.34 – 7.26 (m, 1H), 7.20 (d, J = 8.2 Hz, 1H), 6.93 (d,
J = 8.0 Hz, 1H), 6.75 (s, 1H), 6.50 (d, J = 8.0 Hz, 1H), 5.07 (t, J = 8.8 Hz, 1H), 4.51 – 4.40
(m, 1H), 4.24 (d, J = 15.0 Hz, 1H), 3.89 (s, 3H), 3.81 (t, J = 8.6 Hz, 1H), 3.63 (t, J = 9.2 Hz,
1H), 2.18 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 197.6, 160.0, 150.1, 138.3, 138.2, 129.8,
129.0, 128.5, 127.9, 127.7, 127.2, 127.1, 125.7, 121.7, 120.0, 113.1, 107.6, 56.0, 55.5, 53.8,
48.6, 20.7; IR (KBr, cm-1): 2923, 1618, 1515, 1377, 1178, 787; ESI-HRMS: Calculated for
C24H24NO2 [M+H]+ 358.1802, found 358.1775.
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5.4. 1-(1-benzylindolin-3-yl)ethan-1-one (6d): Yield: 38% (29 mg); Physical appearance:
Yellow oil; TLC Rf 0.3 (19:1, Petroleum ether: EtOAc); 1H NMR (500 MHz, CDCl3): δ 7.39
– 7.30 (m, 5H), 7.21 (d, J = 7.4 Hz, 1H), 7.15 (t, J = 7.6 Hz, 1H), 6.73 (t, J = 7.8 Hz, 1H),
6.57 (d, J = 7.8 Hz, 1H), 4.40 (d, J = 15.0 Hz, 1H), 4.27 (d, J = 15.0 Hz, 1H), 4.10 (dd, J =
13
9.4, 4.8 Hz, 1H), 3.74 (dd, J = 9.4, 4.8 Hz, 1H), 3.50 (d, J = 9.4 Hz, 1H), 2.23 (s, 3H); C
NMR (126 MHz, CDCl3): δ 206.4, 152.2, 137.8, 129.0, 128.6, 127.8, 127.3, 126.7,
125.0,117.9, 107.6, 55.0, 54.6, 53.0, 27.3; IR (KBr, cm-1): 2921, 1715, 1642, 1526, 1385,
1180, 745; ESI-HRMS: Calculated for C17H18NO [M+H]+ 252.1383, found 252.1357.
5.5. (1-benzyl-5-methyl-1H-indol-3-yl)(3-methoxyphenyl)methanone (7a): Yield: 70% (62
o
mg); Physical appearance: Off-white solid, M.p. 106-108 C; TLC Rf 0.3 (19:1, Petroleum
1
ether: EtOAc); H NMR (400 MHz, CDCl3): δ 8.32 (s, 1H), 7.62 (s, 1H), 7.44 – 7.26 (m,
6H), 7.22 (d, J = 8.4 Hz, 1H), 7.19 – 7.07 (m, 4H), 5.35 (s, 2H), 3.87 (s, 3H), 2.51 (s, 3H);
13C NMR (100 MHz, CDCl3): δ 190.6, 159.6, 142.3, 137.4, 135.9, 135.5, 132.6, 129.2, 129.0,
128.1, 127.7, 126.8, 125.4, 122.6, 121.3, 117.4, 115.6, 113.5, 109.9, 55.4, 50.8, 21.5; IR
(KBr, cm-1): 2948, 1620, 1423, 1173, 740; ESI-HRMS: Calculated for C24H22NO2 [M+H]+
356.1645, found 356.1629.
5.6. (1-benzyl-1H-indol-3-yl)(3-methoxyphenyl)methanone (7b): Yield: 68% (58 mg);
Physical appearance: Yellow oil; TLC Rf 0.3 (19:1, Petroleum ether: EtOAc); 1H NMR (400
MHz, CDCl3): δ 8.47 (d, J = 7.5 Hz, 1H), 7.64 (s, 1H), 7.45 – 7.22 (m, 9H), 7.19 – 7.03 (m,
13
3H), 5.32 (s, 2H), 3.82 (s, 3H); C NMR (100 MHz, CDCl3): δ 190.6, 159.6, 142.2, 137.3,
137.2, 135.9, 129.3, 129.0, 128.2, 127.5, 126.9, 123.8, 122.9, 122.9, 121.3, 117.5, 116.0,
113.5, 110.3, 55.4, 50.8; IR (KBr, cm-1): 2953, 1622, 1578, 1463, 1380, 1176, 748; ESI-
HRMS: Calculated for C23H20NO2 [M+H]+ 342.1489, found 342.1463.
5.7. 1-benzyl-1,2,3,5-tetrahydro-4H-benzo[b]azepin-4-one and 1-(1-benzylindolin-3-
yl)ethan-1-one ( 6d and 8a 1:1):30 Yield: 37% (29 mg); Physical appearance: Yellow oil;
1
TLC Rf 0.3 (19:1, Petroleum ether: EtOAc); (Data for 8a) H NMR (400 MHz, CDCl3): δ
7.41 – 7.32 (m, 4H), 7.31 – 7.28 (m, 1H), 7.27 – 7.25 (m, 1H), 7.15 (d, J = 6.6 Hz, 1H), 7.10
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(d, J = 7.8 Hz, 1H), 7.00 (td, J = 7.4, 1.0 Hz, 1H), 4.37 (s, 2H), 3.81 (s, 2H), 3.25 (t, J = 6.6
Hz, 2H), 2.56 (t, J = 6.6 Hz, 2H); IR (KBr, cm-1): 2925, 1651, 1601, 1497, 1360, 1166, 748;
ESI-HRMS: Calculated for C17H18NO [M+H]+ 252.1383, found 252.1373.
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5.8. 1-benzyl-7-methyl-1,2,3,5-tetrahydro-4H-benzo[b]azepin-4-one and 1-(1-benzyl-5-
methylindolin-3-yl)ethan-1-one (6e and 8b 1:1): Yield: 39% (26 mg); Physical appearance:
Yellow oil; TLC Rf 0.3 (19:1, Petroleum ether: EtOAc); 1H NMR (400 MHz, CDCl3): δ 7.42
– 7.35 (m, 8H), 7.35 – 7.29 (m, 2H), 7.14 – 7.08 (m, 1H), 7.07 – 7.01 (m, 2H), 7.01 – 6.96
(m, 2H), 6.51 (d, J = 8.0 Hz, 1H), 4.38 (d, J = 15.0 Hz, 1H), 4.33 (s, 2H), 4.23 (d, J = 15.0
Hz, 1H), 4.06 (dd, J = 9.4, 4.8 Hz, 1H), 3.78 (s, 2H), 3.69 (dd, J = 9.5, 4.8 Hz, 1H), 3.46 (t, J
= 9.4 Hz, 1H), 3.20 (t, J = 6.6 Hz, 2H), 2.54 (d, J = 6.6 Hz, 2H), 2.33 (s, 3H), 2.30 (s, 3H),
2.26 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 209.0, 206.7, 150.2, 146.7, 138.6, 138.0, 132.3,
130.5, 129.8, 129.2, 128.8, 128.6, 128.5, 128.1, 127.8, 127.4, 127.3, 127.2, 127.1, 125.8,
119.4, 107.8, 58.3, 55.5, 54.7, 53.7, 51.4, 48.8, 41.6, 27.3, 20.7, 20.6; IR (KBr, cm-1): 2917,
1730, 1557, 1360, 1221, 735; ESI-HRMS: Calculated for C18H19NONa, [M+Na]+ 288.1359,
found 288.1346.
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AUTHOR INFORMATION
Corresponding Author
mk@iiserb.ac.in
ORCID Manmohan Kapur: 0000-0003-2592-6726
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
Funding from SERB-India (SB/S1/OC-10/2014) and CSIR-India (02(205)/14/EMR-II) is
gratefully acknowledged. GS thanks CSIR-India for a Research Fellowship. MK and DS
thank IISERB for Fellowship. We also thank Director IISERB for funding and infrastructural
facilities.
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge via the Internet at http://pubs.acs.org.
Copies of 1H and 13C spectra for all new compounds (PDF)
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