C-C Bond (Hetero)arylation of Ring-Fused Benzocyclobutenols and Application in the Assembly of Polycyclic Aromatic Hydrocarbons

Article abstract of DOI:10.1021/acs.joc.7b01727

Herein, we disclose a new and efficient synthetic approach to triphenylene-based polycyclic aromatic hydrocarbons (PAHs) from ring-fused benzocyclobutenols (RBCBs) through the cleavage of the C-C σ-bond. Two key transformations are involved: (a) palladium-catalyzed C-C bond (hetero)arylation of RBCBs; and (b) Lewis acid-promoted intramolecular annulation leading to complex polycyclic compounds. A variety of multiply substituted triphenylenes and derivatives are obtained in synthetically useful yields.

Full text of DOI:10.1021/acs.joc.7b01727

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Article
C-C Bond (Hetero)Arylation of Ring-Fused Benzocyclobutenols and
Application in the Assembly of Polycyclic Aromatic Hydrocarbons
Wenbin Mao, and Chen Zhu
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.7b01727 • Publication Date (Web): 11 Aug 2017
Downloaded from http://pubs.acs.org on August 11, 2017
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C-C Bond (Hetero)Arylation of Ring-Fused Benzocyclobutenols and
Application in the Assembly of Polycyclic Aromatic Hydrocarbons
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Wenbin Mao,† and Chen Zhu†,‡,
*
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† Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry,
Chemical Engineering and Materials Science, Soochow University, 199 RenꢀAi Road,
Suzhou, Jiangsu 215123, China.
‡ Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of
Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai
200032, China.
ABSTRACT: Herein we disclose a new and efficient synthetic approach to
triphenyleneꢀbased polycyclic aromatic hydrocarbons (PAHs) from ringꢀfused
benzocyclobutenols (RBCBs) through the cleavage of CꢀC σꢀbond. Two key
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transformations are involved: a) palladiumꢀcatalyzed CꢀC bond (hetero)arylation of
RBCBs; and b) Lewis acidꢀpromoted intramolecular annulation leading to complex
polycyclic compounds. A variety of multiply substituted triphenylenes and derivatives
are obtained in synthetically useful yields.
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Introduction
Polycyclic aromatic hydrocarbons (PAHs) have attracted extensive interest in
interdisciplinary research fields, owing to their unique optical and electrochemical
properties.1 As a branched category of PAHs, triphenylenes have displayed broad
applications in functional organic materials, e.g. OLEDs, liquid crystals, and optical
dataꢀstorage devices.2 Thus, the development of an efficient route to synthesize PAHs
such as triphenylenes is of remarkable significance.3,4
CꢀC bond constitutes the basic framework of organic molecules. Direct elaboration
of CꢀC bond into other chemical bonds represents one of the most ideal and
stepꢀeconomic transformations.5 However, the CꢀC σꢀbond generally remains inert in
the transitionꢀmetal catalyzed reactions mainly due to the unfavorable interaction
between transitionꢀmetal center and CꢀC σꢀorbital engendered by the highly directed
nature of CꢀC bonds.6 Assisted by the ring strain, cyclobutanols frequently serve as
privileged precursors to produce numerous useful organic compounds by breaking the
cyclic CꢀC σꢀbond.7,8,9 As
a
special class of cyclobutanols, ringꢀfused
benzocyclobutenol (RBCB) possesses many salient features: a) oneꢀstep preparation
from readily available aryl bromide and cyclic ketone;10 and b) the presence of
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additional rings that allows for assembly of complex polycyclic compounds. Recently,
we disclosed an iridiumꢀcatalyzed annulation of RBCBs with alkynes through CꢀC
bond cleavage, affording multiply substituted PAHs under mild reaction conditions
(Scheme 1a).11 Prompted by these results, we herein report a new and efficient
synthetic approach to triphenyleneꢀbased PAHs from RBCBs. Two key
transformations, the palladiumꢀcatalyzed CꢀC bond (hetero)arylation of RBCBs and
the Lewis acidꢀpromoted intramolecular annulation leading to complex polycyclic
compounds, are involved. A variety of multiꢀsubstituted triphenylenes and analogues
are furnished in synthetically useful yields (Scheme 1b).
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Scheme 1. Rapid Assembly of PAHs from RBCB
Results and discussion
At the outset, we investigated the ringꢀopening (hetero)arylation of RBCBs. In
2011, Orellana et al. reported an elegant palladiumꢀcatalyzed crossꢀcoupling reaction
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of benzocyclobutenols (BCB) with aryl bromides.12 However, the reaction required
the costly ligand (DavePhos) and stoichiometric amounts of silver salt (Ag2CO3) that
somewhat restricted the practicality of method. Moreover, the reaction substrates
mainly focused on BCBs and the resultant products did not showcase the potential to
construct complex PAHs.13 In this scenario, the development of a new practical
protocol to achieve the CꢀC (hetero)arylation of RBCBs is in demand. Initially, a
variety of transitionꢀmetal catalysts were screened, showing that only palladium
catalysts could promote the desired conversion and [Pd(C3H5)Cl]2 delivered the best
yield. Subsequent survey of reaction parameters led to the optimized reaction
conditions by using PCy3 as ligand, K2CO3 as base, and toluene as solvent (for
detailed reaction conditions survey, see SI). KBr is the only waste of the reaction.
The optimized reaction conditions were subjected to evaluating the generality of
this (hetero)arylation reaction (Scheme 2). Firstly, a set of RBCBs were examined by
varying their framework in the presence of bromobenzene as coupling partner. The
five to eightꢀmembered ringꢀfused BCBs were suitable substrates to generate the
phenylated products 3aꢀ3d. Installation of substituents on the ring did not influence
the conversion (3eꢀ3g). The addition of extra rings to RBCB could easily augment the
product complexity, affording the polycyclic compounds which are otherwise hard to
make (3hꢀ3k). Subsequently, the compatibility of functional groups were investigated.
Both electronꢀdonating and withdrawing groups were well tolerated in the reaction,
consistently delivering good chemical yields (3lꢀ3s). Aside from paraꢀsubstituted
bromobenzene, metaꢀ and orthoꢀsubstituted bromobenzene were apt to give the
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Scheme 2. Generality of Ring-Opening (Hetero)Arylation of RBCB a,b
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aReaction conditions: 1 (0.20 mmol), 2 (0.40 mmol, 2 equiv.), [Pd(C3H5)Cl]2 (0.005
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mmol, 2.5 mol%), PCy3 (0.01 mmol, 5 mol%), and K2CO3 (0.30 mmol, 1.5 equiv.) in
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toluene (2 mL) at 85 C under N2. bYields of isolated products. 85 C for 24 h and
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then 100 oC for the rest time.
coupled products 3t and 3u; the latter was in the form of atropisomers with 1:1 ratio.
In addition, αꢀ and βꢀnaphthylbromide, as well as benzylbromide were also competent
coupling partners (3vꢀ3x). Most importantly, the heteroarylation of RBCBs also
readily proceeded under the current reaction conditions, providing an efficient
approach to incorporate a variety of heteroaryls including the fiveꢀ and sixꢀmembered
heteroaryls into the products, e.g. pyridyl (3y), pyrimidyl (3z), quinolyl (3aa and 3ab),
quinoxalyl (3ac), thienyl (3ad), thiazolyl (3ae), benzofuryl (3af), and benzothienyl
(3ag).
We then turn attention to the intramolecular cyclization of 3 to generate polycyclic
compounds (Scheme 3). Brief survey of reaction conditions revealed that using
Sc(OTf)3 as catalyst could readily give rise to the expected product 4. The only waste
of the transformation is water. While the annulation of cyclohexanone (3b) rapidly
proceeded, the cyclization of cycloheptanone (3c) and cyclooctanone (3d) took much
longer time even at the elevated temperature. The substitution on cyclohexanones
(3eꢀ3g) did not impede theannulation. Benzocyclohexanone (3h) could also undergo
the annulation to give the corresponding product. Varying the substituents on biaryl
part has apparent impact on the reaction that the substrates bearing electronꢀ
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Scheme 3. Acid-Promoted Intramolecular Annulation a,b
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aReaction conditions: 3 (0.20 mmol) and Sc(OTf)3 (0.02 mmol, 10 mol %) in toluene
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(2 mL) at 110 C. bYields of isolated products. Sc(OTf)3 (20 mol %) at 130 C.
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dSc(OTf)3 (30 mol %) at 150 C. Sc(OTf)3 (20 mol %) at 150 C. fSc(OTf)3 (20
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mol %). gTfOH (0.4 mmol, 2 equiv.) in acetonitrile (2 mL) at 85 oC.
withdrawing groups (3nꢀ3q) generally proceeded under the enhanced reaction
conditions, e.g. increased catalyst loading, elevated reaction temperature. Notably, the
cyclization of strong electronꢀdeficient substrates (3r and 3s) was performed in the
presence of stoichiometric amounts of TfOH instead of Lewis acid. In the case of 3t,
the reaction selectively occurred at the paraꢀsite of methyl rather than the orthoꢀsite to
avoid the steric hindrance. The congested orthoꢀsubstituted biphenyl (3u) could also
be tolerated in the reaction. The reaction with naphthyl substrates (3v and 3w) also
displayed good regioselectivity that αꢀposition is preferred than βꢀposition.
Remarkably, the oxygen and sulfurꢀcontaining heteroaryl substrates (3ad, 3af, and
3ag) were also apt to produce the corresponding products efficiently. However, the
nitrogenꢀcontaining heteroaryls (3yꢀ3ac) were not suitable substrates under the
current reaction conditions.
The possible mechanistic pathways for the Lewis acidꢀcatalyzed intramolecular
cyclization of 3 were outlined (Figure 1). According to the experimental results, the
cyclization is dependent upon the high electron density of arene. In this context, the
direct addition of arene to the ketone might take place assisted by the Lewis acid
activation, generating the cationic intermediate I (path a).14 Sequential deprotonation
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of I and dehydration of II afford the polycyclic product 4. Alternatively, the
tautomerization of 3 leads to the enol III, which might undergo 6πꢀelectrocyclization
to yield the cyclized intermediate IV (path b). Dehydration of IV could also generate
the polycyclic product 4.
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Figure 1. Possible mechanistic pathways for Sc(OTf)3ꢀcatalyzed intramolecular
annulation.
With a diverse array of polycyclic precursors in hand, we set about converting them
to PAHs. The aromatization was easily completed in the presence of DDQ, smoothly
generating the resultant PAHs (Scheme 4). A variety of triphenylenes were obtained in
synthetically useful yields regardless of the electron characters of substituents (5aꢀ5j).
In addition to triphenylenes, other derivatives such as benzo[g]chrysene (5k),
phenanthro[9,10ꢀb]thiophene (5m), phenanthro[9,10ꢀb]benzofuran (5n), and
phenanthro[9,10ꢀb]benzothiophene (5o) were also readily prepared. Notably, PAH 5d
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could be obtained from either 4l or 4t; 5k could be furnished from either 4h or 4w.
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Scheme 4. Assembly of Triphenylenes and Derivatives a,b
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o
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a4 (0.20 mmol) and DDQ (0.60 mmol, 3 equiv.) in toluene (2 mL) at 110 C. Yields
of isolate products. cFrom 4h. dFrom 4w. eFrom 4l. fFrom 4t.
Conclusion
In summary, we have described an efficient synthetic approach to
triphenyleneꢀbased PAHs from RBCBs through the palladiumꢀcatalyzed cleavage of
CꢀC σꢀbond. Two key reactions involved in the overall transformation, the
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palladiumꢀcatalyzed CꢀC bond (hetero)arylation of RBCBs and the Lewis
acidꢀpromoted intramolecular annulation leading to complex polycyclic compounds,
are systematically studied. A diverse range of multiꢀsubstituted triphenylenes and
analogues are furnished in synthetically useful yields.
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EXPERIMENT SECTION
General Information. All reactions were maintained under a nitrogen atmosphere.
Commercially available reagents were used without further purification. Chemical
shifts in 1HꢀNMR spectra are reported in ppm from tetramethylsilane with the solvent
resonance as internal standard (CDCl3: δ 7.26). Data are reported as follows: chemical
shift, multiplicity (s = singlet, d = doublet, t = triplet, q = quadruplet, br = broad, m =
multiplet), coupling constants (Hz) and integration. 13CꢀNMR spectra were recorded
with complete proton decoupling. Chemical shifts are reported in ppm from
tetramethylsilane with the solvent resonance as the internal standard (CDCl3: δ 77.16).
Infrared spectra were recorded on an FTIR spectrometer with the absorptions reported
in wavenumbers (cmꢀ1). Products were purified by flash chromatogrgraphy on
300ꢀ400 mesh silica gels. All melting points were determined without correction.
General synthetic procedure of 3. RBCB (0.2 mmol, 1 equiv.), [Pd(C3H5)Cl]2
(0.005 mmol, 2.5 mol %), and PCy3 (0.02 mmol, 10 mol %) were loaded in a flask
which was subjected to evacuation/flushing with nitrogen for three times. Then
freshly distilled anhydrous toluene (2.0 mL) and arylbromide (0.4 mmol, 2 equiv.)
were added to the mixture via syringe. The resultant reaction mixture was kept stirring
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at 85 C until the starting material had been consumed as determined by TLC. Upon
completion of the reaction, the reaction mixture was cooled to room temperature.
After removal of the solvent, the residue was subjected to column chromatography on
silica gel (eluent: ethyl acetate/ petroleum ether) to afford the desired product 3.
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2-([1,1'-biphenyl]-2-yl)cyclopentanone
(3a).
Purification
by
column
chromatography (petroleum ether/EtOAc = 30:1) afforded 3a as a yellow solid (23.4
o
mg, 49%): m.p. 67ꢀ69 C; IR (film, cmꢀ1) 3055, 2923, 2839, 1734, 1669, 1507 cmꢀ1;
1H NMR (400 MHz, CDCl3) δ 7.67ꢀ7.64 (m, 1H), 7.38ꢀ7.27 (m, 5H), 7.24ꢀ7.20 (m,
2H), 6.85ꢀ6.82 (m, 1H), 4.41 (dd, J = 10.8, 4.4 Hz, 1H), 2.83ꢀ2.65 (m, 2H), 2.39ꢀ2.30
(m, 1H), 2.24ꢀ2.15 (m, 1H), 2.05ꢀ1.95 (m, 1H), 1.81ꢀ1.69 (m, 1H); 13C NMR (100
MHz, CDCl3) δ 206.8, 142.3, 141.8, 139.2, 131.3, 128.4, 128.2, 128.1, 127.7, 126.3,
46.6, 40.6, 30.9, 20.0; HRMS [ESIꢀQꢀTOF] calcd for C17H16ONa [M+Na]+ 259.1099,
found 259.1094.
2-([1,1'-biphenyl]-2-yl)cyclohexanone
(3b).
Purification
by
column
chromatography (petroleum ether/EtOAc = 30:1) afforded 3b as a yellow solid (46.1
o
mg, 92%): m.p. 41ꢀ43 C; IR (film, cmꢀ1) 3057, 2939, 2863, 1704, 1597, 1500 cmꢀ1;
1H NMR (400 MHz, CDCl3) δ 7.43ꢀ7.36 (m, 4H), 7.34ꢀ7.26 (m, 3H), 7.26ꢀ7.21 (m,
2H), 3.71 (dd, J = 13.2, 5.6 Hz, 1H), 2.52ꢀ2.46 (m, 1H), 2.31ꢀ2.23 (m, 1H), 2.22ꢀ2.16
(m, 1H), 2.15ꢀ2.06 (m, 1H), 2.02 (dd, J = 12.8, 3.6 Hz, 1H), 1.98ꢀ1.89 (m, 1H),
1.85ꢀ1.72 (m, 1H), 1.70ꢀ1.57 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 210.4, 141.7,
141.1, 136.2, 129.5, 128.6, 128.1, 127.7, 126.9, 126.6, 126.1, 53.8, 41.8, 35.3, 27.2,
25.1; HRMS [ESIꢀQꢀTOF] calcd for C18H18ONa [M+Na]+ 273.1255, found 273.1246.
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2-([1,1'-biphenyl]-2-yl)cycloheptanone
(3c).
Purification
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chromatography (petroleum ether/EtOAc = 30:1) afforded 3c as a yellow solid (46.4
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mg, 88%): m.p. 70ꢀ72 C; IR (film, cmꢀ1) 3060, 2921, 2849, 1699, 1596, 1479 cmꢀ1;
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1H NMR (400 MHz, CDCl3) δ 7.46ꢀ7.32 (m, 5H), 7.32ꢀ7.21 (m, 4H), 3.98 (dd, J =
11.2, 2.8 Hz, 1H), 2.55ꢀ2.46 (m, 1H), 2.41ꢀ2.34 (m, 1H), 2.07ꢀ1.78 (m, 5H), 1.50ꢀ1.28
(m, 3H); 13C NMR (100 MHz, CDCl3) δ 213.6, 141.1, 141.0, 138.9, 129.3, 128.9,
127.7, 127.6, 127.1, 126.6, 125.8, 53.5, 43.4, 32.8, 29.2, 28.9, 23.5; HRMS
[ESIꢀQꢀTOF] calcd for C19H20ONa [M+Na]+ 287.1412, found 287.1422.
2-([1,1'-biphenyl]-2-yl)cyclooctanone
(3d).
Purification
by
column
chromatography (petroleum ether/EtOAc = 30:1) afforded 3d as a colorless oil (46.8
1
mg, 85%): IR (film, cmꢀ1) 3057, 2987, 2924, 1703, 1596, 1497 cmꢀ1; H NMR (400
MHz, CDCl3) δ 7.63 (dd, J = 8.0, 0.8 Hz, 1H), 7.47ꢀ7.35 (m, 4H), 7.29ꢀ7.23 (m, 3H),
7.18 (dd, J = 7.6, 1.2 Hz, 1H), 4.30 (dd, J = 11.6, 3.2 Hz, 1H), 2.27ꢀ2.18 (m, 1H),
2.18ꢀ2.04 (m, 1H), 2.02ꢀ1.88 (m, 2H), 1.75ꢀ1.60 (m, 3H), 1.57ꢀ1.46 (m, 2H),
1.46ꢀ1.33 (m, 2H), 1.32ꢀ1.23 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 216.6, 141.2,
141.2, 137.6, 129.2, 128.9, 127.7, 127.6, 127.2, 126.6, 125.8, 49.32, 43.1, 35.4, 27.9,
25.4, 24.5, 23.6; HRMS [ESIꢀQꢀTOF] calcd for C20H22ONa [M+Na]+ 301.1568,
found 301.1577.
2-([1,1'-biphenyl]-2-yl)-4-(tert-butyl)cyclohexanone (3e). Purification by column
chromatography (petroleum ether/EtOAc = 30:1) afforded 3e as a colorless oil (43.0
1
mg, 70%): IR (film, cmꢀ1) 3052, 2952, 2867, 1715, 1597, 1500 cmꢀ1; H NMR (400
MHz, CDCl3) δ 7.42ꢀ7.34 (m, 4H), 7.34ꢀ7.25 (m, 3H), 7.25ꢀ7.19 (m, 2H), 3.69 (dd, J
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= 13.2, 4.8 Hz, 1H), 2.51ꢀ2.45 (m, 1H), 2.33ꢀ2.22 (m, 1H), 2.20ꢀ2.14 (m, 1H),
2.13ꢀ2.06 (m, 1H), 1.85ꢀ1.75 (m, 1H), 1.62ꢀ1.52 (m, 2H), 0.90 (s, 9H); 13C NMR (100
MHz, CDCl3) δ 210.8, 141.6, 141.0, 136.4, 129.5, 128.5, 128.1, 127.7, 126.9, 126.6,
126.1, 53.0, 46.7, 41.1, 36.5, 32.0, 27.9, 27.1; HRMS [ESIꢀQꢀTOF] calcd for
C22H26ONa [M+Na]+ 329.1881, found 329.1886.
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2-([1,1'-biphenyl]-2-yl)-4-phenylcyclohexanone (3f). Purification by column
chromatography (petroleum ether/EtOAc = 30:1) afforded 3f as a colorless oil (47.8
1
mg, 73%): IR (film, cmꢀ1) 2987, 2972, 2901, 1713, 1653, 1597 cmꢀ1; H NMR (400
MHz, CDCl3) δ 7.45ꢀ7.36 (m, 4H), 7.33ꢀ7.28 (m, 4H), 7.27ꢀ7.19 (m, 6H), 3.92 (dd, J
= 11.6, 6.8 Hz, 1H), 3.12ꢀ3.04 (m, 1H), 2.63ꢀ2.56 (m, 1H), 2.54ꢀ2.44 (m, 1H),
2.34ꢀ2.22 (m, 3H), 2.12ꢀ2.00 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 209.7, 143.8,
141.7, 141.0, 135.6, 129.5, 128.6, 128.1, 128.1, 127.8, 127.0, 126.7, 126.3, 126.2,
53.1, 42.8, 42.2, 41.3, 34.2; HRMS [ESIꢀQꢀTOF] calcd for C24H22ONa [M+Na]+
349.1568, found 349.1569.
2-([1,1'-biphenyl]-2-yl)-4,4-dimethylcyclohexanone (3g). Purification by column
chromatography (petroleum ether/EtOAc = 30:1) afforded 3g as a white solid (45.9
o
mg, 82%): m.p. 55ꢀ57 C; IR (film, cmꢀ1) 3025, 2955, 2850, 1714, 1597, 1498 cmꢀ1;
1H NMR (400 MHz, CDCl3) δ 7.42ꢀ7.33 (m, 4H), 7.33ꢀ7.21 (m, 5H), 3.91 (dd, J =
13.2, 5.2 Hz, 1H), 2.44ꢀ2.29 (m, 2H), 1.97 (dd, J = 13.2, 13.2 Hz, 1H), 1.87ꢀ1.80 (m,
1H), 1.77ꢀ1.67 (m, 2H), 1.03 (s, 3H), 1.02 (s, 3H); 13C NMR (100 MHz, CDCl3) δ
210.6, 141.7, 140.9, 136.0, 129.3, 128.5, 128.4, 127.7, 126.9, 126.6, 126.1, 49.0, 48.2,
39.1, 37.9, 31.0, 30.6, 23.4; HRMS [ESIꢀQꢀTOF] calcd for C20H22ONa [M+Na]+
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301.1568, found 301.1577.
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2-([1,1'-biphenyl]-2-yl)-3,4-dihydronaphthalen-1(2H)-one (3h). Purification by
column chromatography (petroleum ether/EtOAc = 30:1) afforded 3h as a yellow
solid (54.5 mg, 91%): m.p. 113ꢀ114 oC; IR (film, cmꢀ1) 3054, 2920, 2896, 1678, 1596,
1498 cmꢀ1; 1H NMR (400 MHz, CDCl3) δ 8.09 (dd, J = 7.6, 0.8 Hz, 1H), 7.48 (ddd, J
= 7.6, 7.6, 1.2 Hz, 1H), 7.41ꢀ7.29 (m, 9H), 7.25ꢀ7.20 (m, 2H), 3.96 (dd, J = 13.2, 4.8
Hz, 1H), 2.99ꢀ2.94 (m, 2H), 2.48ꢀ2.36 (m, 1H), 2.28ꢀ2.21 (m, 1H); 13C NMR (100
MHz, CDCl3) δ 198.5, 143.6, 142.1, 141.0, 137.8, 132.9, 132.5, 129.6, 128.8, 128.3,
127.7, 127.6, 127.2, 126.6, 126.2, 126.2, 51.2, 31.5, 29.1; HRMS [ESIꢀQꢀTOF] calcd
for C22H18ONa [M+Na]+ 321.1255, found 321.1264.
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2-(1-phenylnaphthalen-2-yl)cyclohexanone (3i). Purification by column
chromatography (petroleum ether/EtOAc = 30:1) afforded 3i as a colorless oil (47.9
1
mg, 80%): IR (film, cmꢀ1) 3063, 2919, 2850, 1741, 1508, 1491 cmꢀ1; H NMR (400
MHz, CDCl3) δ 7.91ꢀ7.84 (m, 2H), 7.53ꢀ7.48 (m, 1H), 7.48ꢀ7.42 (m, 3H), 7.42ꢀ7.38
(m, 1H), 7.36ꢀ7.30 (m, 2H), 7.30ꢀ7.25 (m, 1H), 7.22ꢀ7.18 (m, 1H), 3.56 (dd, J = 12.8,
5.6 Hz, 1H), 2.50ꢀ2.43 (m, 1H), 2.25ꢀ2.14 (m, 2H), 2.14ꢀ2.02 (m, 2H), 1.96ꢀ1.88 (m,
1H), 1.84ꢀ1.71 (m, 1H), 1.66ꢀ1.53 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 210.3,
138.7, 138.2, 134.1, 132.4, 131.9, 129.8, 129.3, 128.1, 127.8, 127.3, 127.0, 126.9,
126.2, 125.7, 125.2, 124.9, 54.8, 41.7, 35.1, 27.0, 25.0; HRMS [ESIꢀQꢀTOF] calcd for
C22H20ONa [M+Na]+ 323.1412, found 323.1420.
2-(10-phenylphenanthren-9-yl)cyclohexanone (3j). Purification by column
chromatography (petroleum ether/EtOAc = 30:1) afforded 3j as a white solid (51.9
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mg, 74%): m.p. 230ꢀ232 oC; IR (film, cmꢀ1) 3065, 2921, 2879, 1733, 1680, 1575 cmꢀ1;
1H NMR (400 MHz, CDCl3) δ 8.81 (d, J = 8.4 Hz, 1H), 8.74 (d, J = 8.4 Hz, 1H),
7.67ꢀ7.57 (m, 4H), 7.56ꢀ7.48 (m, 3H), 7.44ꢀ7.39 (m, 1H), 7.34ꢀ7.27 (m, 3H), 3.80 (dd,
J = 12.0, 6.8 Hz, 1H), 2.73ꢀ2.65 (m, 1H), 2.55ꢀ2.43 (m, 1H), 2.36ꢀ2.26 (m, 1H),
2.17ꢀ2.05 (m, 2H), 2.03ꢀ1.93 (m, 2H), 1.56ꢀ1.47 (m, 1H); 13C NMR (100 MHz,
CDCl3) δ 209.6, 139.9, 138.4, 132.4, 131.6, 130.7, 129.5, 129.5, 129.0, 128.5, 128.3,
128.0, 127.5, 127.2, 127.1, 125.9, 125.8, 125.5, 125.5, 123.0, 121.9, 54.5, 40.9, 32.2,
24.8, 24.6; HRMS [ESIꢀQꢀTOF] calcd for C26H23O [M+H]+ 351.1749, found
351.1741.
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2-(10-phenylphenanthren-9-yl)-3,4-dihydronaphthalen-1(2H)-one (3k). Purification
by column chromatography (petroleum ether/EtOAc = 30:1) afforded 3k as a yellow
solid (55.4 mg, 70%): m.p. 251ꢀ253 oC; IR (film, cmꢀ1) 3065, 2921, 2879, 1733, 1680,
1575 cmꢀ1; 1H NMR (400 MHz, CDCl3) δ 8.80 (d, J = 8.4 Hz, 1H), 8.75 (d, J = 8.4 Hz,
1H), 8.17 (d, J = 6.8 Hz, 1H), 7.65ꢀ7.58 (m, 2H), 7.57ꢀ7.41 (m, 8H), 7.40ꢀ7.34 (m,
3H), 7.28 (d, J = 8.0 Hz, 1H), 4.18ꢀ4.11 (m, 1H), 3.00ꢀ2.85 (m, 3H), 2.24ꢀ2.16 (m,
1H); 13C NMR (100 MHz, CDCl3) δ 197.4, 143.4, 140.0, 139.0, 133.3, 133.1, 132.1,
131.6, 130.7, 129.8, 129.5, 129.1, 128.6, 128.3, 128.3, 127.9, 127.6, 127.4, 127.1,
126.5, 125.9, 125.9, 125.8, 125.5, 123.0, 121.9, 53.1, 29.9, 29.6; HRMS [ESIꢀQꢀTOF]
calcd for C30H23O [M+H]+ 399.1749, found 399.1741.
2-(4'-methyl-[1,1'-biphenyl]-2-yl)cyclohexanone (3l). Purification by column
chromatography (petroleum ether/EtOAc = 30:1) afforded 3l as a white solid (46.8
o
mg, 89%): m.p. 70ꢀ72 C; IR (film, cmꢀ1) 3056, 2933, 2862, 1708, 1516, 1483 cmꢀ1;
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1H NMR (400 MHz, CDCl3) δ 7.41ꢀ7.36 (m, 1H), 7.33ꢀ7.30 (m, 1H), 7.30ꢀ7.19 (m,
4H), 7.13 (d, J = 8.0 Hz, 2H), 3.75 (dd, J = 13.2, 5.6 Hz, 1H), 2.53ꢀ2.47 (m, 1H), 2.43
(s, 3H), 2.33ꢀ2.24 (m, 1H), 2.22ꢀ2.06 (m, 2H), 2.02 (dd, J = 12.8, 3.6 Hz, 1H),
1.99ꢀ1.88 (m, 1H), 1.86ꢀ1.73 (m, 1H), 1.72ꢀ1.59 (m, 1H); 13C NMR (100 MHz,
CDCl3) δ 210.5, 141.6, 138.1, 136.3, 136.2, 129.6, 128.4, 128.1, 126.7, 126.1, 53.8,
41.8, 35.4, 27.2, 25.1, 20.7; HRMS [ESIꢀQꢀTOF] calcd for C19H20ONa [M+Na]+
287.1412, found 287.1402.
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2-(4'-methoxy-[1,1'-biphenyl]-2-yl)cyclohexanone (3m). Purification by column
chromatography (petroleum ether/EtOAc = 30:1) afforded 3m as a yellow solid (45.5
o
mg, 81%): m.p. 54ꢀ56 C; IR (film, cmꢀ1) 3056, 2957, 2853, 1703, 1608, 1578 cmꢀ1;
1H NMR (400 MHz, CDCl3) δ 7.39ꢀ7.33 (m, 1H), 7.31ꢀ7.21 (m, 3H), 7.13 (d, J = 8.8
Hz, 2H), 6.92 (d, J = 8.8 Hz, 2H), 3.86 (s, 3H), 3.72 (dd, J = 12.8, 5.6 Hz, 1H),
2.52ꢀ2.44 (m, 1H), 2.32ꢀ2.22 (m, 1H), 2.20ꢀ2.07 (m, 2H), 2.07ꢀ1.89 (m, 2H),
1.84ꢀ1.71 (m, 1H), 1.70ꢀ1.58 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 210.5, 158.2,
141.3, 136.4, 133.4, 129.6, 129.6, 128.1, 126.7, 126.1, 113.1, 54.8, 53.8, 41.8, 35.3,
27.2, 25.2; HRMS [ESIꢀQꢀTOF] calcd for C19H20O2Na [M+Na]+ 303.1361, found
303.1352.
2-(4'-fluoro-[1,1'-biphenyl]-2-yl)cyclohexanone (3n). Purification by column
chromatography (petroleum ether/EtOAc = 30:1) afforded 3n as a yellow solid (40.3
mg, 75%): m.p. 74ꢀ76 oC; IR (film, cmꢀ1) 3056, 2934, 2863, 1703, 1598, 1514 cmꢀ1;
1H NMR (400 MHz, CDCl3) δ 7.35ꢀ7.31 (m, 1H), 7.27ꢀ7.19 (m, 2H), 7.17ꢀ7.09 (m,
3H), 7.06ꢀ6.98 (m, 2H), 3.57 (dd, J = 12.8, 5.6 Hz, 1H), 2.46ꢀ2.39 (m, 1H), 2.24ꢀ2.14
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(m, 1H), 2.14ꢀ2.03 (m, 2H), 2.02ꢀ1.92 (m, 1H), 1.92ꢀ1.84 (m, 1H), 1.79ꢀ1.65 (m, 1H),
1.64ꢀ1.52 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 210.8, 162.1 (d, JCꢀF = 246.0 Hz),
141.1, 137.5 (d, JCꢀF = 3.4 Hz), 136.8, 130.6 (d, JCꢀF = 7.9 Hz), 130.0, 128.6, 127.6,
126.6, 115.1 (d, JCꢀF = 21.3 Hz), 54.3, 42.3, 35.6, 27.6, 25.6; 19F NMR (376 MHz,
CDCl3) δ ꢀ115.6 (s); HRMS [ESIꢀQꢀTOF] calcd for C18H17OFNa [M+Na]+ 291.1161,
found 291.1152.
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2-(4'-chloro-[1,1'-biphenyl]-2-yl)cyclohexanone (3o). Purification by column
chromatography (petroleum ether/EtOAc = 30:1) afforded 3o as a yellow solid (50.7
o
mg, 89%): m.p. 80ꢀ82 C; IR (film, cmꢀ1) 3066, 2955, 2864, 1702, 1646, 1593 cmꢀ1;
1H NMR (400 MHz, CDCl3) δ 7.40ꢀ7.32 (m, 3H), 7.30ꢀ7.22 (m, 2H), 7.18 (dd, J = 7.6,
1.2 Hz, 1H), 7.12 (d, J = 8.4 Hz, 2H), 3.60 (dd, J = 12.8, 5.2 Hz, 1H), 2.49ꢀ2.42 (m,
1H), 2.29ꢀ2.18 (m, 1H), 2.18ꢀ2.06 (m, 2H), 2.05ꢀ1.96 (m, 1H), 1.95ꢀ1.88 (m, 1H),
1.82ꢀ1.69 (m, 1H), 1.68ꢀ1.55 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 210.3, 140.4,
139.5, 136.2, 132.7, 129.9, 129.3, 128.2, 127.9, 127.3, 126.2, 53.8, 41.8, 35.1, 27.2,
25.1; HRMS [ESIꢀQꢀTOF] calcd for C18H17OClNa [M+Na]+ 307.0866, found
307.0876.
2-(4'-(trifluoromethyl)-[1,1'-biphenyl]-2-yl)cyclohexanone (3p). Purification by
column chromatography (petroleum ether/EtOAc = 30:1) afforded 3p as a white solid
o
(53.8 mg, 85%): m.p. 96ꢀ98 C; IR (film, cmꢀ1) 3062, 2933, 2859, 1710, 1615, 1478
1
cmꢀ1; H NMR (400 MHz, CDCl3) δ 7.65 (d, J = 8.0 Hz, 2H), 7.45ꢀ7.39 (m, 1H),
7.36ꢀ7.27 (m, 4H), 7.21 (dd, J = 7.6, 1.2 Hz, 1H), 3.58 (dd, J = 12.8, 5.6 Hz, 1H),
2.52ꢀ2.46 (m, 1H), 2.30ꢀ2.20 (m, 1H), 2.20ꢀ2.07 (m, 2H), 2.03 (dd, J = 12.8, 3.6 Hz,
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1H), 1.99ꢀ1.91 (m, 1H), 1.84ꢀ1.71 (m, 1H), 1.70ꢀ1.61 (m, 1H); C NMR (100 MHz,
CDCl3) δ 210.6, 145.3, 140.7, 136.6, 129.7, 129.4 (q, JCꢀF = 32.2 Hz), 129.4, 128.8,
128.1, 126.8, 125.2 (q, JCꢀF = 3.8 Hz), 124.2 (q, JCꢀF = 270.3 Hz), 54.2, 42.2, 35.6,
27.6, 25.5; 19F NMR (376 MHz, CDCl3) δ ꢀ62.4 (s); HRMS [ESIꢀQꢀTOF] calcd for
C19H17OF3Na [M+Na]+ 341.1129, found 341.1125.
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Methyl 2'-(2-oxocyclohexyl)-[1,1'-biphenyl]-4-carboxylate (3q). Purification by
column chromatography (petroleum ether/EtOAc = 30:1) afforded 3q as a white solid
(53.1 mg, 86%): m.p. 126ꢀ128 oC; IR (film, cmꢀ1) 3052, 2939, 2860, 1718, 1608, 1558
cmꢀ1; H NMR (400 MHz, CDCl3) δ 8.06 (d, J = 8.4 Hz, 2H), 7.43ꢀ7.38 (m, 1H),
1
7.34ꢀ7.26 (m, 4H), 7.22 (dd, J = 7.6, 1.2 Hz, 1H), 3.94 (s, 3H), 3.60 (dd, J = 12.8, 5.6
Hz, 1H), 2.50ꢀ2.44 (m, 1H), 2.27ꢀ2.19 (m, 1H), 2.19ꢀ2.04 (m, 2H), 2.01 (dd, J = 12.8,
3.6 Hz, 1H), 1.97ꢀ1.88 (m, 1H), 1.82ꢀ1.71 (m, 1H), 1.66ꢀ1.54 (m, 1H); 13C NMR (100
MHz, CDCl3) δ 210.1, 166.5, 145.9, 140.6, 136.0, 129.1, 129.0, 128.7, 128.5, 128.3,
127.5, 126.2, 53.8, 51.7, 41.7, 35.2, 27.1, 25.1; HRMS [ESIꢀQꢀTOF] calcd for
C20H20O3Na [M+Na]+ 331.1310, found 331.1311.
2'-(2-oxocyclohexyl)-[1,1'-biphenyl]-4-carbonitrile (3r). Purification by column
chromatography (petroleum ether/EtOAc = 30:1) afforded 3r as a white solid (49.5
mg, 90%): m.p. 118ꢀ120 C; IR (film, cmꢀ1) 3046, 2921, 2850, 2225, 1705, 1646,
o
1505 cmꢀ1; 1H NMR (400 MHz, CDCl3) δ 7.68 (d, J = 8.4 Hz, 2H), 7.45ꢀ7.40 (m, 1H),
7.35ꢀ7.27 (m, 4H), 7.18 (dd, J = 7.6, 1.2 Hz, 1H), 3.52 (dd, J = 12.8, 5.2 Hz, 1H),
2.51ꢀ2.45 (m, 1H), 2.28ꢀ2.20 (m, 1H), 2.20ꢀ2.08 (m, 2H), 2.08ꢀ1.99 (m, 1H),
1.99ꢀ1.91 (m, 1H), 1.83ꢀ1.71 (m, 1H), 1.69ꢀ1.56 (m, 1H); 13C NMR (100 MHz,
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CDCl3) δ 210.4, 146.4, 140.3, 136.4, 132.0, 129.9, 129.5, 128.8, 128.4, 126.9, 118.8,
111.1, 54.3, 42.2, 35.5, 27.5, 25.5; HRMS [ESIꢀQꢀTOF] calcd for C19H17ONNa
[M+Na]+ 298.1208, found 298.1213.
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2-(4'-nitro-[1,1'-biphenyl]-2-yl)cyclohexanone (3s). Purification by column
chromatography (petroleum ether/EtOAc = 30:1) afforded 3s as a white solid (54.7
mg, 92%): m.p. 163ꢀ165 oC; IR (film, cmꢀ1) 3056, 2931, 2866, 1700, 1593, 1509 cmꢀ1;
1H NMR (400 MHz, CDCl3) δ 8.25 (d, J = 8.8 Hz, 2H), 7.47ꢀ7.42 (m, 1H), 7.39 (d, J
= 8.8 Hz, 2H), 7.36ꢀ7.32 (m, 1H), 7.31ꢀ7.28 (m, 1H), 7.21 (dd, J = 7.6, 1.2 Hz, 1H),
3.53 (dd, J = 12.8, 5.6 Hz, 1H), 2.46ꢀ2.52 (m, 1H), 2.28ꢀ2.20 (m, 1H), 2.20ꢀ2.07 (m,
2H), 2.04 (dd, J = 12.8, 3.6 Hz, 1H), 2.00ꢀ1.90 (m, 1H), 1.84ꢀ1.71 (m, 1H), 1.69ꢀ1.57
(m, 1H); 13C NMR (100 MHz, CDCl3) δ 209.9, 148.0, 146.6, 139.4, 136.0, 129.5,
129.0, 128.4, 128.1, 126.4, 123.0, 53.8, 41.7, 35.0, 27.0, 25.0; HRMS [ESIꢀQꢀTOF]
calcd for C18H18O3N [M+H]+ 296.1287, found 296.1272.
2-(3'-methyl-[1,1'-biphenyl]-2-yl)cyclohexanone (3t). Purification by column
chromatography (petroleum ether/EtOAc = 30:1) afforded 3t as a colorless oil (40.7
1
mg, 77%): IR (film, cmꢀ1) 3055, 2969, 2863, 1710, 1604, 1584 cmꢀ1; H NMR (400
MHz, CDCl3) δ 7.41ꢀ7.36 (m, 1H), 7.33ꢀ7.23 (m, 4H), 7.17 (d, J = 7.6 Hz, 1H),
7.05ꢀ6.99 (m, 2H), 3.72 (dd, J = 12.8, 5.2 Hz, 1H), 2.52ꢀ2.46 (m, 1H), 2.39 (s, 3H),
2.32ꢀ2.22 (m, 1H), 2.22ꢀ2.05 (m, 2H), 2.02 (dd, J = 12.8, 3.6 Hz, 1H), 1.97ꢀ1.89 (m,
1H), 1.85ꢀ1.72 (m, 1H), 1.70ꢀ1.58 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 210.5,
141.7, 141.0, 137.3, 136.2, 129.4, 129.3, 128.1, 127.5, 127.3, 126.8, 126.0, 125.6,
53.8, 41.8, 35.4, 27.2, 25.1, 21.0; HRMS [ESIꢀQꢀTOF] calcd for C19H21O [M+H]+
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265.1592, found 265.1581.
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2-(2'-methyl-[1,1'-biphenyl]-2-yl)cyclohexanone (3u). Purification by column
chromatography (petroleum ether/EtOAc = 30:1) afforded 3u as a white solid (48.8
mg, 92%, d.r. 1:1): m.p. 63ꢀ65 oC; IR (film, cmꢀ1) 3060, 2932, 2860, 1711, 1597, 1574
cmꢀ1; 1H NMR (400 MHz, CDCl3) δ 7.41ꢀ7.35 (m, 2H, one isomer), 7.32ꢀ7.20 (m, 9H,
two isomers), 7.18ꢀ7.11 (m, 3H, two isomers), 7.09 (d, J = 7.2 Hz, 1H, one isomer),
6.99 (d, J = 7.2 Hz, 1H, one isomer), 3.41 (dd, J = 12.8, 5.6 Hz, 1H, one isomer), 3.35
(dd, J = 12.8, 5.6 Hz, 1H, one isomer), 2.47ꢀ2.37 (m, 2H, two isomers), 2.25ꢀ2.18 (m,
1H, one isomer), 2.18ꢀ2.10 (m, 3H, two isomers), 2.10ꢀ2.01 (m, 3H, two isomers),
2.07 (s, 3H), 1.98 (s, 3H), 1.96ꢀ1.84 (m, 3H, two isomers), 1.84ꢀ1.71 (m, 2H, two
isomers), 1.71ꢀ1.51 (m, 2H, two isomers); 13C NMR (100 MHz, CDCl3) δ 210.0 &
209.8 (two isomers), 140.9 & 140.8 (two isomers), 140.3 & 140.3 (two isomers),
136.8 & 136.5 (two isomers), 136.3 & 135.0 (two isomers), 129.5 & 129.3 (two
isomers), 129.2 & 129.0 (two isomers), 129.0 & 128.7 (two isomers), 128.6 & 127.6
(two isomers), 126.9 & 126.9 (two isomers), 126.9 & 126.8 (two isomers), 126.0 &
126.0 (two isomers), 125.1 & 124.9 (two isomers), 53.8 & 53.5 (two isomers), 41.8 &
41.7 (two isomers), 36.0 & 34.5 (two isomers), 27.2 & 27.0 (two isomers), 25.2 &
25.0 (two isomers), 19.8 & 19.5 (two isomers); HRMS [ESIꢀQꢀTOF] calcd for
C19H20ONa [M+Na]+ 287.1412, found 287.1407.
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2-(2-(naphthalen-2-yl)phenyl)cyclohexanone (3v). Purification by column
chromatography (petroleum ether/EtOAc = 30:1) afforded 3v as a yellow oil (53.6 mg,
89%): IR (film, cmꢀ1) 3054, 2933, 2860, 1708, 1629, 1597 cmꢀ1; 1H NMR (400 MHz,
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CDCl3) δ 7.94ꢀ7.84 (m, 3H), 7.72 (s, 1H), 7.57ꢀ7.52 (m, 2H), 7.48ꢀ7.41 (m, 1H),
7.40ꢀ7.31 (m, 4H), 3.76 (dd, J = 13.2, 5.6 Hz, 1H), 2.53ꢀ2.46 (m, 1H), 2.28ꢀ2.17 (m,
2H), 2.12ꢀ1.99 (m, 2H), 1.95ꢀ1.88 (m, 1H), 1.85ꢀ1.71 (m, 1H), 1.67ꢀ1.52 (m, 1H); 13C
NMR (100 MHz, CDCl3) δ 210.5, 141.6, 138.6, 136.4, 132.8, 131.9, 129.7, 128.2,
127.6, 127.3, 127.1, 127.0, 126.2, 125.9, 125.6, 53.9, 41.8, 35.4, 27.2, 25.1; HRMS
[ESIꢀQꢀTOF] calcd for C22H20ONa [M+Na]+ 323.1412, found 323.1401.
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2-(2-(naphthalen-1-yl)phenyl)cyclohexanone (3w). Purification by column
chromatography (petroleum ether/EtOAc = 30:1) afforded 3w as a colorless oil (52.8
mg, 88%, d.r. 1:1): IR (film, cmꢀ1) 3057, 2922, 2852, 1709, 1545, 1505 cmꢀ1; 1H NMR
(400 MHz, CDCl3) δ 7.94ꢀ7.84 (m, 4H, two isomers), 7.55ꢀ7.43 (m, 8H, two isomers),
7.42ꢀ7.30 (m, 7H, two isomers), 7.27ꢀ7.22 (m, 3H, two isomers), 3.33 (dd, J = 12.4,
5.6 Hz, 1H, one isomer), 3.30 (dd, J = 12.4, 5.6 Hz, 1H, one isomer), 2.39ꢀ2.27 (m,
2H, two isomers), 2.15ꢀ2.05 (m, 2H, two isomers), 2.05ꢀ1.92 (m, 4H, two isomers),
1.92ꢀ1.84 (m, 2H, two isomers), 1.83ꢀ1.75 (m, 2H, two isomers), 1.74ꢀ1.62 (m, 2H,
13
two isomers), 1.46ꢀ1.30 (m, 2H, two isomers); C NMR (100 MHz, CDCl3) δ 210.3
& 209.7 (two isomers), 139.5 & 139.4 (two isomers), 138.5 & 138.3 (two isomers),
137.7 & 137.5 (two isomers), 133.0 & 132.8 (two isomers), 132.1 & 131.8 (two
isomers), 130.1 & 130.1 (two isomers), 128.8 & 127.7 (two isomers), 127.7 & 127.4
(two isomers), 127.2 & 127.2 (two isomers), 127.1 & 127.1 (overlap, two isomers),
126.7 & 126.2 (two isomers), 126.0 & 126.0 (two isomers), 126.0 & 125.8 (two
isomers), 125.5 & 125.5 (two isomers), 125.4 & 125.3 (two isomers), 124.8 & 124.7
(two isomers), 54.0 & 53.8 (two isomers), 41.7 & 41.7 (two isomers), 36.5 & 34.7
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(two isomers), 27.2 & 27.1 (two isomers), 25.0 & 25.0 (two isomers); HRMS
[ESIꢀQꢀTOF] calcd for C22H21O [M+H]+ 301.1592, found 301.1591.
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Methyl 4-(2-(2-oxocyclohexyl)benzyl)benzoate (3x). Purification by column
chromatography (petroleum ether/EtOAc = 30:1) afforded 3x as a yellow solid (51.3
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60
o
mg, 80%): m.p. 97ꢀ99 C; IR (film, cmꢀ1) 3062, 2923, 2851, 1711, 1673, 1573 cmꢀ1;
1H NMR (400 MHz, CDCl3) δ 7.94 (d, J = 8.4 Hz, 2H), 7.32ꢀ7.27 (m, 1H), 7.25ꢀ7.21
(m, 1H), 7.19ꢀ7.12 (m, 4H), 3.97 (s, 2H), 3.90 (s, 3H), 3.70 (dd, J = 12.0, 5.6 Hz, 1H),
2.50ꢀ2.44 (m, 1H), 2.35ꢀ2.26 (m, 1H), 2.16ꢀ2.07 (m, 1H), 2.06ꢀ1.97 (m, 1H),
1.97ꢀ1.87 (m, 2H), 1.81ꢀ1.69 (m, 1H), 1.66ꢀ1.58 (m, 1H); 13C NMR (100 MHz,
CDCl3) δ 209.3, 166.5, 145.7, 137.2, 137.0, 130.2, 129.3, 128.4, 128.1, 127.7, 126.6,
126.5, 53.1, 51.6, 42.0, 39.1, 34.5, 27.2, 25.3; HRMS [ESIꢀQꢀTOF] calcd for
C21H23O3 [M+H]+ 323.1647, found 323.1639.
2-(2-(pyridin-3-yl)phenyl)cyclohexanone
(3y).
Purification
by
column
chromatography (petroleum ether/EtOAc = 30:1) afforded 3y as a yellow solid (35.1
o
mg, 70%): m.p. 95ꢀ97 C; IR (film, cmꢀ1) 3059, 2932, 2852, 1711, 1477, 1444 cmꢀ1;
1H NMR (400 MHz, CDCl3) δ 8.60 (dd, J = 4.8, 1.6 Hz, 1H), 8.49 (d, J = 1.6 Hz, 1H),
7.55ꢀ7.51 (m, 1H), 7.45ꢀ7.39 (m, 1H), 7.36ꢀ7.27 (m, 3H), 7.23ꢀ7.19 (m, 1H), 3.57 (dd,
J = 12.8, 5.2 Hz, 1H), 2.50ꢀ2.43 (m, 1H), 2.28ꢀ2.15 (m, 2H), 2.14ꢀ2.05 (m, 1H),
2.04ꢀ1.98 (m, 1H), 1.98ꢀ1.90 (m, 1H), 1.83ꢀ1.56 (m, 2H); 13C NMR (100 MHz,
CDCl3) δ 209.9, 149.1, 147.9, 137.8, 136.7, 136.5, 136.1, 129.6, 128.3, 127.8, 126.4,
122.6, 53.7, 41.7, 35.1, 27.2, 25.0; HRMS [ESIꢀQꢀTOF] calcd for C17H17ONNa
[M+Na]+ 274.1208, found 274.1222.
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2-(2-(pyrimidin-5-yl)phenyl)cyclohexanone (3z). Purification by column
chromatography (petroleum ether/EtOAc = 30:1) afforded 3z as a white solid (30.0
mg, 60%): m.p. 117ꢀ119 oC; IR (film, cmꢀ1) 3056, 2939, 2863, 1704, 1597, 1500 cmꢀ1;
1H NMR (400 MHz, CDCl3) δ 9.21 (s, 1H), 8.62 (s, 2H), 7.49ꢀ7.44 (m, 1H), 7.39ꢀ7.34
(m, 1H), 7.32 (d, J = 8.0 Hz, 1H) 7.20 (dd, J = 7.6, 0.8 Hz, 1H), 3.49 (dd, J = 12.8,
5.2 Hz, 1H), 2.52ꢀ2.45 (m, 1H), 2.29ꢀ2.16 (m, 2H), 2.15ꢀ2.07 (m, 1H), 2.04 (dd, J =
12.8, 3.6 Hz, 1H), 1.99ꢀ1.92 (m, 1H), 1.82ꢀ1.72 (m, 1H), 1.72ꢀ1.61 (m, 1H); 13C NMR
(100 MHz, CDCl3) δ 209.4, 157.1, 156.0, 136.7, 134.6, 134.0, 129.6, 128.6, 126.7,
53.7, 41.7, 35.0, 27.0, 25.0; HRMS [ESIꢀQꢀTOF] calcd for C16H17ON2 [M+H]+
253.1341, found 253.1334.
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2-(2-(quinolin-2-yl)phenyl)cyclohexanone (3aa). Purification by column
chromatography (petroleum ether/EtOAc = 30:1) afforded 3aa as a yellow solid (46.9
o
mg, 78%): m.p. 83ꢀ85 C; IR (film, cmꢀ1) 3055, 2936, 2848, 1771, 1636, 1576 cmꢀ1;
1H NMR (400 MHz, CDCl3) δ 8.20 (d, J = 8.4 Hz, 1H), 8.10 (d, J = 8.4 Hz, 1H), 7.86
(d, J = 8.0 Hz, 1H), 7.77ꢀ7.72 (m, 1H), 7.59ꢀ7.51 (m, 3H), 7.49ꢀ7.44 (m, 1H),
7.42ꢀ7.36 (m, 2H), 4.24 (dd, J = 13.2, 5.2 Hz, 1H), 2.49ꢀ2.38 (m, 2H), 2.32ꢀ2.23 (m,
13
1H), 2.14ꢀ2.02 (m, 2H), 2.00ꢀ1.92 (m, 1H), 1.85ꢀ1.60 (m, 2H); C NMR (100 MHz,
CDCl3) δ 210.3, 159.4, 147.1, 139.9, 136.9, 136.0, 129.5, 129.2, 129.0, 128.5, 128.1,
127.1, 126.4, 126.2, 126.0, 121.9, 53.6, 42.0, 34.8, 27.5, 25.3; HRMS [ESIꢀQꢀTOF]
calcd for C21H20ON [M+H]+ 302.1545, found 302.1553.
2-(2-(isoquinolin-4-yl)phenyl)cyclohexanone (3ab). Purification by column
chromatography (petroleum ether/EtOAc = 30:1) afforded 3ab as a brown oil (53.9
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mg, 90%, d.r. 1.3:1): IR (film, cmꢀ1) 3057, 2932, 2860, 1707, 1620, 1503 cmꢀ1; H
NMR (400 MHz, CDCl3) δ 9.28 (s, 2.3H, two isomers), 8.39 (s, 1.3H, one isomer),
8.29 (s, 1H, one isomer), 8.07ꢀ7.99 (m, 2.3H, two isomers), 7.66ꢀ7.60 (m, 2.3H, two
isomers), 7.60ꢀ7.53 (m, 2.3H, two isomers), 7.52ꢀ7.43 (m, 4.6H, two isomers),
7.39ꢀ7.34 (m, 4.6H, two isomers), 7.26ꢀ7.22 (m, 2.3H, two isomers), 3.33ꢀ3.25 (m,
2.3H, two isomers), 2.42ꢀ2.35 (m, 1H, one isomer), 2.33ꢀ2.28 (m, 1.3H, one isomer),
2.17ꢀ1.76 (m, 11.5H, two isomers), 1.75ꢀ1.60 (m, 2H, one isomer), 1.49ꢀ1.28 (m,
2.6H, one isomer); 13C NMR (100 MHz, CDCl3) δ 209.5 & 209.5 (two isomers),
151.8 & 151.7 (two isomers), 142.7 & 142.2 (two isomers), 138.1 & 137.9 (two
isomers), 135.6 & 135.6 (two isomers), 134.8 & 134.6 (two isomers), 131.9 & 131.5
(two isomers), 130.4 & 130.4 (two isomers), 130.3 & 130.1 (two isomers), 128.9 &
128.2 (two isomers), 127.9 & 127.8 (two isomers), 127.7 & 127.6 (two isomers),
127.4 & 127.1 (two isomers), 127.0 & 126.8 (two isomers), 126.2 & 126.2 (two
isomers), 124.8 & 124.3 (two isomers), 53.9 & 53.8 (two isomers), 41.6 & 41.6
(overlap, two isomers), 36.3 & 35.0 (two isomers) , 27.1 & 27.0 (two isomers) , 25.0
& 24.9 (two isomers); HRMS [ESIꢀQꢀTOF] calcd for C21H20ON [M+H]+ 302.1545,
found 302.1554; ESI [M+H]+ 302.1.
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2-(2-(quinazolin-2-yl)phenyl)cyclohexanone (3ac). Purification by column
chromatography (petroleum ether/EtOAc = 30:1) afforded 3ac as a brown solid (49.4
mg, 82%): m.p. 91ꢀ93 C; IR (film, cmꢀ1) 3060, 2919, 2851, 1740, 1699, 1547 cmꢀ1;
o
1H NMR (400 MHz, CDCl3) δ 9.00 (s, 1H), 8.16ꢀ8.12 (m, 1H), 8.09ꢀ8.05 (m, 1H),
7.82ꢀ7.75 (m, 2H), 7.59 (dd, J = 7.6, 1.2 Hz, 1H), 7.54ꢀ7.49 (m, 1H), 7.46ꢀ7.40 (m,
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2H), 4.22 (dd, J = 13.2, 5.2 Hz, 1H), 2.52ꢀ2.46 (m, 1H), 2.44ꢀ2.37 (m, 1H), 2.37ꢀ2.28
(m, 1H), 2.16ꢀ2.04 (m, 2H), 2.01ꢀ1.94 (m, 1H), 1.85ꢀ1.76 (m, 1H), 1.75ꢀ1.66 (m, 1H);
13C NMR (100 MHz, CDCl3) δ 209.7, 154.0, 145.5, 141.0, 140.5, 137.6, 136.2, 129.9,
129.7, 129.4, 129.0, 129.0, 128.9, 128.8, 126.7, 53.4, 41.9, 34.8, 27.4, 25.3; HRMS
[ESIꢀQꢀTOF] calcd for C20H19ON2 [M+H]+ 303.1497, found 303.1496.
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2-(2-(thiophen-2-yl)phenyl)cyclohexanone (3ad). Purification by column
chromatography (petroleum ether/EtOAc = 30:1) afforded 3ad as a yellow solid (32.3
o
mg, 63%): m.p. 52ꢀ54 C; IR (film, cmꢀ1) 2987, 2958, 2834, 1702, 1647, 1578 cmꢀ1;
1H NMR (400 MHz, CDCl3) δ 7.41ꢀ7.37 (m, 2H), 7.34 (dd, J = 5.2, 1.2 Hz, 1H),
7.31ꢀ7.26 (m, 2H), 7.07 (dd, J = 5.2, 3.6 Hz, 1H), 6.89 (dd, J = 3.6, 1.2 Hz, 1H), 3.94
(dd, J = 13.2, 5.2 Hz, 1H), 2.55ꢀ2.48 (m, 1H), 2.40ꢀ2.30 (m, 1H), 2.27ꢀ2.20 (m, 1H),
2.19ꢀ2.10 (m, 1H), 2.09ꢀ1.92 (m, 2H), 1.86ꢀ1.65 (m, 2H); 13C NMR (100 MHz,
CDCl3) δ 210.1, 141.9, 137.4, 133.9, 130.7, 128.2, 127.7, 126.6, 126.2, 126.1, 125.1,
53.8, 41.8, 35.2, 27.2, 25.1; HRMS [ESIꢀQꢀTOF] calcd for C16H16OSNa [M+Na]+
279.0820, found 279.0829.
2-(2-(thiazol-5-yl)phenyl)cyclohexanone
(3ae).
Purification
by
column
chromatography (petroleum ether/EtOAc = 30:1) afforded 3ae as a yellow solid (27.0
o
mg, 53%): m.p. 90ꢀ92 C; IR (film, cmꢀ1) 3061, 2923, 2861, 1698, 1598, 1522 cmꢀ1;
1H NMR (400 MHz, CDCl3) δ 8.83 (s, 1H), 7.68 (s, 1H), 7.45ꢀ7.40 (m, 1H), 7.36ꢀ7.28
(m, 3H), 3.77 (dd, J = 13.2, 5.2 Hz, 1H), 2.54ꢀ2.47 (m, 1H), 2.37ꢀ2.28 (m, 1H),
2.25ꢀ2.10 (m, 2H), 2.08ꢀ1.94 (m, 2H), 1.81ꢀ1.67 (m, 2H); 13C NMR (100 MHz,
CDCl3) δ 210.1, 153.4, 141.8, 138.3, 136.7, 131.4, 130.2, 129.0, 128.8, 126.8, 54.3,
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42.2, 35.4, 27.6, 25.5; HRMS [ESIꢀQꢀTOF] calcd for C15H16ONS [M+H]+ 258.0953,
found 258.0956.
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2-(2-(benzofuran-3-yl)phenyl)cyclohexanone (3af). Purification by column
chromatography (petroleum ether/EtOAc = 30:1) afforded 3af as a brown solid (29.0
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mg, 50%): m.p. 92ꢀ94 C; IR (film, cmꢀ1) 3056, 2936, 2834, 1703, 1616, 1571 cmꢀ1;
1H NMR (400 MHz, CDCl3) δ 7.56ꢀ7.53 (m, 1H), 7.50 (s, 1H), 7.47ꢀ7.42 (m, 1H),
7.39ꢀ7.31 (m, 5H), 7.25ꢀ7.20 (m, 1H), 3.77 (dd, J = 12.8, 5.6 Hz, 1H), 2.50ꢀ2.44 (m,
1H), 2.26ꢀ2.13 (m, 2H), 2.12ꢀ1.95 (m, 2H), 1.93ꢀ1.86 (m, 1H), 1.82ꢀ1.69 (m, 1H),
13
1.65ꢀ1.53 (m, 1H); C NMR (100 MHz, CDCl3) δ 210.5, 154.5, 141.7, 137.9, 130.3,
130.3, 128.4, 127.8, 127.6, 126.4, 124.1, 122.6, 120.5, 119.7, 111.1, 54.0, 41.8, 35.3,
27.1, 25.1; HRMS [ESIꢀQꢀTOF] calcd for C20H19O2 [M+H]+ 291.1385, found
291.1379.
2-(2-(benzo[b]thiophen-3-yl)phenyl)cyclohexanone (3ag). Purification by column
chromatography (petroleum ether/EtOAc = 30:1) afforded 3ag as a colorless oil (41.9
mg, 68%, d.r. 1:1): IR (film, cmꢀ1) 3059, 2933, 2859, 1707, 1601, 1524 cmꢀ1; 1H NMR
(400 MHz, CDCl3) δ 7.96ꢀ7.88 (m, 2H, two isomers), 7.49ꢀ7.25 (m, 15H, two
isomers), 7.17 (s, 1H, one isomer), 3.57ꢀ3.50 (m, 2H, two isomers), 2.48ꢀ2.35 (m, 2H,
two isomers), 2.22ꢀ1.97 (m, 7H, two isomers), 1.92ꢀ1.65 (m, 5H, two isomers),
1.58ꢀ1.43 (m, 2H, two isomers); 13C NMR (100 MHz, CDCl3) δ 210.6 & 210.0 (two
isomers), 139.5 & 139.1 (two isomers), 139.1 & 138.9 (two isomers), 138.1 & 138.0
(two isomers), 136.6 & 135.9 (two isomers), 135.0 & 134.6 (two isomers), 130.3 &
130.0 (two isomers), 129.2 & 127.7 (two isomers), 127.6 & 127.6 (overlap, two
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isomers), 126.3 & 126.3 (overlap, two isomers), 124.0 & 124.0 (two isomers), 123.8
& 123.4 (two isomers), 122.8 & 122.3 (two isomers), 122.3 & 122.1 (two isomers),
54.0 & 54.0 (two isomers), 41.8 & 41.8 (overlap, two isomers), 36.4 & 34.4 (two
isomers), 27.2 & 27.0 (two isomers), 25.0 & 25.0 (overlap, two isomers); HRMS
[ESIꢀQꢀTOF] calcd for C20H19OS [M+H]+ 307.1157, found 307.1149.
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General synthetic procedure of 4. Compound 3 (0.2 mmol) and Sc(OTf)3 (0.02
mmol 10 mol %) were dissolved in the freshly distilled anhydrous toluene (2 mL),
o
and then the reaction mixture was kept stirring at 110 C (unless otherwise noted)
until the starting material had been consumed as determined by TLC. At the end of the
reaction, the reaction mixture was cooled to room temperature. After removal of the
solvent, the residue was subjected to column chromatography on silica gel (eluent:
ethyl acetate/ petroleum ether) to afford the desired product 4.
1,2,3,4-tetrahydrotriphenylene (4b). Purification by column chromatography
o
(petroleum ether) afforded 4b as a white solid (42.3 mg, 92%): m.p. 118ꢀ120 C; IR
(film, cmꢀ1) 3073, 2924, 2849, 1591, 1493, 1434 cmꢀ1; 1H NMR (400 MHz, CDCl3) δ
8.74ꢀ8.69 (m, 2H), 8.10ꢀ8.05 (m, 2H), 7.66ꢀ7.59 (m, 4H), 3.21ꢀ3.14 (m, 4H),
13
2.06ꢀ1.97 (m, 4H); C NMR (100 MHz, CDCl3) δ 132.0, 130.3, 129.3, 126.6, 125.5,
123.3, 122.7, 26.9, 23.0; HRMS [CIꢀQꢀTOF] calcd for C18H17 [M+H]+ 233.1330,
found 233.1335.
10,11,12,13-tetrahydro-9H-cyclohepta[l]phenanthrene (4c). Purification by column
chromatography (petroleum ether) afforded 4c as a white solid (42.3 mg, 86%): m.p.
o
162ꢀ164 C; IR (film, cmꢀ1) 3076, 2988, 2843, 1585, 1498, 1474 cmꢀ1; 1H NMR (400
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MHz, CDCl3) δ 8.76ꢀ8.80 (m, 2H), 8.27ꢀ8.21 (m, 2H), 7.69ꢀ7.59 (m, 4H), 3.43ꢀ3.38
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7
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(m, 4H), 1.98ꢀ1.91 m, 2H), 1.81ꢀ1.73 (m, 4H); C NMR (100 MHz, CDCl3) δ 136.8,
8
9
130.9, 129.6, 126.6, 125.3, 123.9, 123.1, 31.3, 28.0, 26.2; HRMS [CIꢀQꢀTOF] calcd
for C19H19 [M+H]+ 247.1487, found 247.1481.
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9,10,11,12,13,14-hexahydrocycloocta[l]phenanthrene (4d). Purification by column
chromatography (petroleum ether) afforded 4d as a white solid (31.2 mg, 60%): m.p.
o
159ꢀ161 C; IR (film, cmꢀ1) 3076, 2960, 2846, 1607, 1585, 1492 cmꢀ1; 1H NMR (400
MHz, CDCl3) δ 8.80ꢀ8.73 (m, 2H), 8.22ꢀ8.15 (m, 2H), 7.68ꢀ7.60 (m, 4H), 3.48ꢀ3.38
(m, 4H), 1.97ꢀ1.85 (m, 4H), 1.49ꢀ1.40 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 134.1,
130.8, 129.9, 126.6, 125.4, 124.6, 123.0, 30.5, 27.4, 26.8; HRMS [CIꢀQꢀTOF] calcd
for C20H21 [M+H]+ 261.1643, found 261.1649.
2-(tert-butyl)-1,2,3,4-tetrahydrotriphenylene (4e). Purification by column
chromatography (petroleum ether) afforded 4e as a white solid (50.9 mg, 88%): m.p.
o
125ꢀ127 C; IR (film, cmꢀ1) 3076, 2926, 2864, 1605, 1491, 1473 cmꢀ1; 1H NMR (400
MHz, CDCl3) δ 8.75ꢀ8.68 (m, 2H), 8.17ꢀ8.11 (m, 1H), 8.09ꢀ8.03 (m, 1H), 7.69ꢀ7.60
(m, 4H), 3.41ꢀ3.25 (m, 2H), 3.09ꢀ2.98 (m, 1H), 2.90ꢀ2.80 (m, 1H), 2.29ꢀ2.20 (m, 1H),
1.67ꢀ1.57 (m, 1H), 1.53ꢀ1.40 (m, 1H), 1.13 (s, 9H); 13C NMR (100 MHz, CDCl3) δ
132.2, 131.8, 130.5, 130.3, 129.4, 129.2, 126.6, 126.6, 125.5, 123.5, 123.3, 122.8,
122.7, 44.4, 32.6, 28.6, 28.3, 27.5, 24.3; HRMS [CIꢀQꢀTOF] calcd for C22H25 [M+H]+
289.1956, found 289.1961.
2-phenyl-1,2,3,4-tetrahydrotriphenylene
(4f).
Purification
by
column
chromatography (petroleum ether) afforded 4f as a white solid (45.6 mg, 74%): m.p.
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