Copper-catalyzed electrosynthesis of 1-acyl-2,2-diphenylcyclopropanes and their behaviour in acidic medium

Article abstract of DOI:10.1016/S0040-4020(02)01620-4

The formation of 1-acyl-2,2-diphenylcyclopropanes is performed under mild electrochemical conditions. These cyclopropane derivatives, through acid-catalyzed ring-opening, lead to γ,γ-diphenyl-β,γ-unsaturated carbonyl compounds which evolve into either substituted naphthalenes, or β-benzhydryl-α,β-cycloalkenones depending on the acyclic or cyclic nature of the intermediate allyl ketone.

Full text of DOI:10.1016/S0040-4020(02)01620-4

Tetrahedron 59 (2003) 1073–1081
Copper-catalyzed electrosynthesis of 1-acyl-2,2-diphenyl-
cyclopropanes and their behaviour in acidic medium
*
Sylvain Oudeyer, Eric Leonel, Jean Paul Paugam and Jean-Yves Nedelec
´
´ ´
` ´
Laboratoire d’Electrochimie, Catalyse et Synthese Organique, UMR 7582, CNRS-Universite Paris XII Val de Marne, 2, Rue Henri Dunant,
B.P. 28, F-94320 Thiais, France
Received 28 May 2002; revised 30 September 2002; accepted 10 December 2002
Abstract—The formation of 1-acyl-2,2-diphenylcyclopropanes is performed under mild electrochemical conditions. These cyclopropane
derivatives, through acid-catalyzed ring-opening, lead to g,g-diphenyl-b,g-unsaturated carbonyl compounds which evolve into either
substituted naphthalenes, or b-benzhydryl-a,b-cycloalkenones depending on the acyclic or cyclic nature of the intermediate allyl
ketone. q 2003 Elsevier Science Ltd. All rights reserved.
1. Introduction
coupling process, now applied to a,b-unsaturated ketones or
aldehydes and dichlorodiphenylmethane. It has already
been shown that nucleophilic ring opening of acylcyclo-
propanes is a useful route to prepare 1,4-difunctional
compounds.2a,b In this study, we have found that, under
acidic treatment, 1-acyl-2,2-diphenylcyclopropanes can be
converted into allyl ketones which are new routes to
substituted naphthalenes or to b-benzhydryl-a,b-cyclo-
alkenones.
We have previously investigated the synthesis of cyclopro-
panes by direct electroreductive cyclocondensation between
a,a,a-trichloro or gem-dihalo compounds and a,b-unsatu-
rated carboxylic esters. This method, however, only applies
to activated olefins which are more easily reduced than the
polyhalo compound.1a We have more recently found a way
to get round this limitation by setting up a method involving
the indirect electrochemical activation of the halo com-
pound, through either a Fe/Ni catalyst in the case of non-
activated gem-dibromocompounds1b (dibromomethane,
2,2-dibromopropane, 1,1-dibromoethane) or a Fe/Cu cata-
lyst in the case of activated a,a,a-trichloro or gem-
dichlorocompounds1c (methyltrichloroacetate, a,a,a-tri-
chlorotoluene, benzal chloride, dichlorodiphenylmethane).
A brief description of these most recent results is given in
Equation (1a).
2. Results and discussion
2.1. Cyclopropane formation
The cyclocondensations (Eq. (1b)) are conducted, as
previously described,1c in an undivided cell fitted with an
XC10 iron rod (iron containing 0.1% of carbon) as the
anode and a nickel foam as the cathode. A solution of
copper bromide (1 mmol) and Bu4NBr (300 mg) in DMF
(45 mL) and pyridine (5 mL) is first electrolyzed at constant
current intensity (0.3 A) during 15 min at 25.T.2108C.
Then the a,b-unsaturated ketone or aldehyde (10 mmol)
and dichlorodiphenylmethane (20 mmol) are added, and the
ð1aÞ
In this paper, we develop the synthesis of 1-acyl-2,2-
diphenylcyclopropanes, based on the same electroreductive
Keywords: acyl cyclopropanes; b-benzhydryl-a,b-cycloalkenones;
substituted naphthalenes; electro-organic synthesis; benzannulation.
*
Corresponding author. Tel.: þ1-49-78-11-26; fax: þ1-49-78-11-48;
(1b)
e-mail: paugam@glvt-cnrs.fr
0040–4020/03/$ - see front matter q 2003 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020(02)01620-4

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S. Oudeyer et al. / Tetrahedron 59 (2003) 1073–1081
solution is electrolyzed (0.1 A) until complete consumption
of the carbonyl compound (about 8 h).
saturated ketones,2c or to its 1,3-dipolar addition followed
by a ring-contraction of the pyrazolines.3a,b,4,9 Surprisingly,
in the literature, 1-acetyl-2,2-diphenylcyclopropane 2 is
prepared in three steps via methyl6 or ethyl8 2,2-diphenyl-
cyclopropane carboxylate and subsequent treatment with
KOH, HCl and methyllithium7,8 (Eq. (3)). Diphenyldiazo-
methane is possibly basic enough to deprotonate methyl-
vinylketone.
Our results are listed in Table 1. The by-products are
reduction or dimerisation derivatives of dichlorodiphenyl-
methane, i.e. diphenylmethane, benzhydryl chloride, and
tetraphenylethylene. As for the couple dimethylitaconate–
dichlorodiphenylmethane selected as model reagents in
Ref. 1c, the influence of several parameters on the yield and
selectivity of the cyclopropanation has been examined on
the cyclohexenone–dichlorodiphenymethane model system
(Table 1, entry 4), i.e. the reagents ratio, the reaction
temperature, the DMF-pyridine ratio, the current intensity
during the electrolysis, the CuBr-reagents ratio, and the
charge required for the formation of Cu(0) and, possibly,
Fe(0) during the pre-electrolysis. Only the two last
parameters led to some effects in regard to the previous
results. Thus, on the one hand, in the absence of CuBr, the
cyclopropane yield was down to 51% instead of 76% (Table
1, entry 4), but tetraphenylethylene, benzhydryl chloride
and diphenylmethane remain minor products while they
previously became major products in Ref. 1c (traces of
cyclopropane). On the other hand, when the pre-electrolysis
was carried on beyond 15 min (Table 1, entry 4), the yield of
cyclopropane was slightly increased (þ4%). Consequently,
we examined the effect of the duration of the pre-
electrolysis for every model, and found that the cyclopro-
pane yield increased significantly only for the mixture
chalcone-dichlorodiphenylmethane (from 25 to 41%, Table
1, entry 1). With the optimized conditions, isolated yields
are in the range of 34–81% (Table 1, entries 1–7).
ð3Þ
2.2. Acid-catalyzed ring-opening
Subsequent acid catalyzed isomerization to g,g-diphenyl-
b,g-unsaturated ketones was carried out as follows: to a
solution of 1-acyl-2,2-diphenylcyclopropane (250 mg in
25 mL glacial acetic acid) was added 0.5 mL of 12N
hydrochloric acid. The reaction was monitored by GC
analysis. In the case of slow isomerization, the reaction
mixture was heated at reflux.
The cyclopropane adducts are obtained from the a,b-un-
saturated ketones with high stereoselectivity. With acyclic
enones no cis-1-acyl-2,2-diphenylcyclopropane was
detected by GC–MS, (Table 1, entry 1 and 3). As expected,
also, no trans-cyclopropane derivative was formed with
cyclic enones (Table 1, entries 4–6). Within these two
series, the cyclisation is also regiospecific as no oxirane was
formed. On the contrary, with crotonaldehyde (Table 1,
entry 7 and Eq. (2)), the cyclocondensation gave a 74/26
mixture of cyclopropane and oxirane and, in addition, the
cyclopropanation gave a cis/trans ratio of 45/55. The
oxirane 7b was characterized by GC–MS and NMR.
Our results, in agreement with the work of Lutz et al.2c
about the preparation of 1,3,4,4-tetraphenylbut-3-en-1-one
8 from 1-benzoyl-2,2,3-triphenylcyclopropane 1 in acidic
medium are reported in Table 2, entries 1 and 3: g,g-Di-
phenyl-b,g-unsaturated ketones 8 and 10 are obtained by
acid-catalyzed isomerization of 1-acyl-2,2-diphenylcyclo-
propanes 1 (AcOH, reflux) and 2 (AcOH, rt), respectively
(Eq. (4)).
ð4Þ
When 1-acetyl-2,2,3-triphenylcyclopropane 3 (Table 2,
entry 5) or 1-formyl-3-methyl-2,2-diphenylcyclopropane 7
(Table 2, entry 7) was treated at room temperature, the
expected g,g-diphenyl-b,g-unsaturated carbonyl compound
was actually formed, as indicated by GC–MS analysis, but
another product was also observed, which became the only
product after heating at reflux. These products were
characterized as naphthalene derivatives, i.e. 1,2-diphenyl-
4-methylnaphthalene 13 and 2-methyl-1-phenylnaphthalene
15 (Table 2, entries 6 and 8). By similar treatment,
the g,g-diphenyl-b,g-unsaturated ketones 8 and 10 also
lead to respectively 1,2,4-triphenylnaphthalene 9 and
ð2Þ
These electrosyntheses are a good alternative to the
photocondensation of diphenyldiazomethane with a,b-un-

S. Oudeyer et al. / Tetrahedron 59 (2003) 1073–1081
1075
Table 1. 1-Acyl-2,2-diphenylcyclopropane formation by copper catalyzed indirect electroreductive coupling of activated olefins and dichlorodiphenylmethane
Entry
Olefin
1-Acyl-2,2-diphenyl-
cyclopropane
Nr
Isolated
yield (%)
CAS RN
Melting
point (8C)
Melting point 8C,
yield% in literature
25
41a
100–103,4 354
125–127,2c 202c
1
1
[10266-31-6]
125–126
58–59,5 386,7
bp2,5¼159–160,7,8 538
2
2
40
[27067-40-9]
58–59
3
3
41
New compound
136–138
New compound
76
4
5
6
4
5
6
80a
51b
New compound
94–95
New compound
105–106,9 259
New compound
81
[22524-16-9]
108–109
51
New compound
67–68
New compounds
cis/trans: 55/45
cis: 94–96
trans: not isolated
7
7
34
New compounds
a
Pre-electrolysis: 30 mn, 0.3 A.
Pre-electrolysis without CuBr.
b
4-methyl-1-phenylnapthalene 11 (Table 2, entries 2 and 4).
This acid catalyzed isomerization followed by a benzannu-
lation is, to our knowledge, a new route to naphthalene
derivatives (Eq. (5)).
by multistep syntheses (11,13,14,19,20 1521), or by nickel-
catalyzed coupling of Grignard reagents with naphthyl-
bromide derivative (1516), or by palladium-catalyzed
annulation of internal alkynes by arene-containing vinyl
iodides (911).
The formation of 4-methyl-1,2-diphenylnapthalene 13 (new
compound) from 3 can be explained as shown in Equation
(6). The intermediate 12 is very likely formed, but rapidly
transformed via its protonated form.
The acid catalyzed isomerization of the two bicyclic ketones
4 and 5 leads respectively to 3-benzhydrylcyclohex-2-enone
17 and to 3-benzhydrylcyclopent-2-enone 19 via the
expected g,g-diphenyl-b,g-unsaturated ketones 16 and 18
which are thermodynamically less stable as they have an
These naphthalene compounds are usually prepared either

1076
S. Oudeyer et al. / Tetrahedron 59 (2003) 1073–1081
(5)
(6)
exocyclic double bond (Table 2, entries 9–12). In the case
of 8,8-diphenylbicyclo[5.1.0]octan-2-one 6 (Table 2, entry
13) the two isomeric exo/endo enones 20 and 21 are
obtained in 73/27 ratio, this ratio did not change even after
prolonged heating, though the yields decrease, respectively,
to 44 and 16% instead of 61 and 24% (Eq. (7)).
Up to now, only multistep syntheses of 17 and 19 are
described in the literature, as shown in Equation (8).17,18
ð8Þ
ð7Þ
No naphthalenic compounds are formed, likely because the
rigidity of the cyclic b,g-unsaturated ketones should prevent
it to get the appropriate geometry for the benzannulation
reaction. In brief, the acyclic allyl ketones, in acidic
medium, are converted into substituted naphthalenes and
the cyclic allyl ketones in b-benzhydryl-a,b-cyclo-
alkenones via the corresponding 3-benzhydrylidene-
cycloalkanones. Our results are listed in Table 2.
3. Conclusion
This paper presents an interesting method of formation of
1-acyl-2,2-diphenylcyclopropanes under mild electro-
chemical reaction conditions. The monocyclic compounds
obtained proved to be new synthons of naphthalene
derivatives through acid catalyzed sequential ring-opening/

S. Oudeyer et al. / Tetrahedron 59 (2003) 1073–1081
Table 2. Acidic transformations of 1-acyl-2,2-diphenylcyclopropanes
1077
Entry 1-Acyl-2,2-diphenyl- Nr
cyclopropane
Reaction time,
temperature
Product
Nr
Isolated
yield%
CAS RN
Melting
point (8C)
Melting point 8C
in literature
1
2
3
4
1
1
2
2
3 h, 1208C
48 h, 1208C
30 min, rt
8
81
[53449-11-9]
195–196
158–160
50–51
193.5–1982c
159–16111
51–5212a
9
20
[806-58-6]
10 51
[55004-95-0]
15 h, 1208C
11 60
[13280-69-8]
37–38
38.5–3913
Not
isolateda
5
3
4 h, rt
12
[7593-09-1]
147.5–148.515
6
3
3 h, 1208C
13 72
New compound 139–140
New compound
Not
isolateda
7
7
14
8
7
4 h 15 min, 1208C
15 33
[29304-63-0]
43–44
4416a
(continued on next page)

1078
S. Oudeyer et al. / Tetrahedron 59 (2003) 1073–1081
Table 2 (continued)
Entry 1-Acyl-2,2-diphenyl- Nr
cyclopropane
Reaction time,
temperature
Product
Nr
Isolated
yield%
CAS RN
Melting
point (8C)
Melting point 8C
in literature
Not
isolatedb
9
4
3 h, rt
16
10
11
12
4
5
5
17 67
[21086-47-5]
Oil
bp0.2: 170–18017
Not
isolatedb
25 h, rt
18
19 58
[70239-00-8]
68–69
68.5–69.518
61
20
13
6
30 min, 1208C
New compound 74–75
New compound
44c
24
21
New compound 91–92
New coumpound
16c
a
The g,g-diphenyl-b,g-unsaturated ketone or aldehyde undergoes a very fast cyclisation leading to the substituted naphthalene and, therefore, cannot be
isolated.
The g,g-diphenyl-b,g-unsaturated ketone presents an exocyclic double bond and is rapidly converted into the stable isomer with the endocyclic double bond.
1208C, 7 h.
b
c
benzannulation. In the case of bicyclic derivatives, the acid-
pounds, which was observed as a side reaction in the
presence of crotonaldehyde.
catalyzed ring-opening leads to the corresponding 3-benz-
hydrylidene-5-, 6-, or 7-membered-cycloalkanone. These
compounds, which have an exocyclic double bond, are
completely (the two first cases) or partially (last case)
converted into endocyclic double bond isomers. Therefore,
the two consecutive reactions (cyclopropanation and acid
catalyzed isomerization) can efficiently replace a Heck
type reaction in the preparation of b-benzhydryl-a,b-
cycloalkenones.
4. Experimental
4.1. General information
Melting points were determined with an Electrothermal IA
9100 digital melting point apparatus. 1H, 13C NMR spectra
were recorded on a Bruker AC-200 (200, 50 MHz
respectively) or Bruker AM-300 (300, 75 MHz respec-
tively) spectrometer. Mass spectra (electron impact) were
obtained on a GCQ Thermoquest spectrometer equipped
with a DB 5MS capillary column. Infrared spectra
were recorded on a Perkin–Elmer Spectrum BX FT-IR
spectrometer. High-resolution mass spectral analyses and
The cyclopropanation may result from a conjugated
addition followed by SNi or may involve a metallocarbene
species. This remains to be elucidated by electrochemical
analyses. We are now investigating the formation of
oxiranes by copper indirect electroreductive coupling of
aldehydes or ketones and activated gem-dichlorocom-

S. Oudeyer et al. / Tetrahedron 59 (2003) 1073–1081
1079
elemental analyses were carried out at ‘Service Central
d’Analyse du CNRS’, Vernaison, France. Gas chroma-
tography was performed on a Varian 3300 chromatograph
fitted with a SIL-5 CP capillary column. Solvents and
chemicals were used as received. The XC10 Fe rod (iron
269 (base peak), 268, 192, 191, 165, 105, 91, 77, 65, 50. IR4
n (cm21) (CCl4) 3075, 3035, 1675, 1600, 1580, 1495, 1445.
4.3.2. 1-Acetyl-2,2-diphenylcyclopropane 2. (C17H16O);
MW: 236.314; CAS RN: 27067-40-9. Pentane (aluminium
oxide—90 active, neutral (activity I)); obtained: 0.945 g
(yield: 40%, method a); mp: 58–598C. 1H NMR8
(200 MHz, CDCl3) d 7.40–7.00 (Ph, 10H, m), 2.80 (H-1,
1H, dd, J¼7.9, 6.3 Hz), 2.25 (H-3a, 1H, dd, J¼6.3, 4.2 Hz),
´
with 0.1% of carbon) is purchased from Weber Metaux.
4.2. General procedure
Method a, indirect electrochemical process with Fe anode
in the presence of CuBr. The reactions are conducted in an
undivided cell fitted with an Fe rod as the anode and a nickel
foam as the cathode (area: ca. 40 cm2). A solution of CuBr
(144 mg, 1 mmol) and Bu4NBr (300 mg) in DMF (45 mL)
and pyridine (5 mL) is electrolysed at constant current
intensity (0.3 A) during 15 min at 25.T.2108C. Then,
the activated olefin (10 mmol) and the dichlorodiphenyl-
methane (20 mmol) are added and electrolysed (0.1 A) until
the complete consumption of the olefin (about 8 h). The
DMF is evaporated under reduced pressure. The reaction
mixture is poured into a cold mixture of 1 M HCl (50 mL)
and diethyl ether (50 mL). The layers are separated and
extracted with diethyl ether (three portions of 25 mL). The
combined ethereal extracts are washed with a saturated
solution of ammonium chloride and brine, dried over
MgSO4. Products are isolated either by column chroma-
tography on silica gel (230–400 mesh) or aluminium oxide
(70–230 mesh) using pentane-ether as eluent or by flash
chromatography on aluminium oxide (70–230 mesh) using
pentane–dichloromethane as eluent.
2.10 (CH3, 3H, s), 1.50 (H-3b, 1H, dd, J¼7.9, 4.2 Hz). 13
C
NMR8 (50 MHz, CDCl3) d CO: 203.7; C(Ph): 145.0, 139.4,
129.9, 129.4, 128.4, 128.3, 128.2, 127.5, 127.2, 127.0,
126.5; C-2: 42.7; C-1, CH3: 37.1, 31.1; C-3: 21.0. EI-MS
m/z: 236, 221, 194, 193 (base peak), 179, 178, 166, 165,
116, 115; IR8 n (cm21) (CH2Cl2) 3060, 2990, 1705, 1605,
1585, 1500, 1460, 1440, 1430.
4.3.3. trans-1-Acetyl-2,2,3-triphenylcyclopropane 3 (new
compound). (C23H20O); MW: 312.412; Anal. calcd for
C23H20O: C, 88.43; H, 6.45; O, 5.12. Found: C, 88.21; H,
6.36; O, 5.15. Pentane/ether: (99/1)–(95/5); obtained:
1
1.28 g (yield: 41%, method a); mp: 136–1388C. H NMR
(200 MHz, CDCl3) d 7.50–7.00 (Ph, 15H, m), 3.90 (H-3,
1H, d, J¼6.3 Hz), 3.50 (H-1, 1H, d, J¼6.3 Hz), 2.40 (CH3,
3H, s). 13C NMR (50 MHz, CDCl3) d CO: 203.4; C(Ph):
141.3, 140.4, 136.3, 129.8, 129.2, 128.5, 128.2, 128.0,
127.9, 127.4, 127.0, 126.6, 126.3; C-2: 51.1; C-1, C-3, CH3:
40.8, 35.6, 31.4. EI-MS m/z 270, 269, 192, 191 (base peak),
190, 189, 165, 91; IR n (cm21) (CH2Cl2) 3060, 2990, 1705,
1605, 1585, 1500, 1450.
Method b, chemical isomerization and benzannulation
process. The reactions are performed in a two-necked
round bottom flask fitted with a condenser. To 250 mg of
1-acyl-2,2-diphenylcyclopropane is added a mixture of
glacial acetic acid (2.5 mL) and hydrochloric acid 37%
(0.5 mL). The solution is stirred at rt (products 10, 17, 19)
or at 1208C (products 8, 9, 11, 13, 15, 20, 21). The
isomerization and the benzannulation reactions are moni-
tored by GC analysis (see reaction time in Table 2). When
reaction time is longer than 5 h at 1208C, small amounts of
acetic acid and HCl must be added, from time to time, in
order to maintain the acidic conditions (pH 1). The mixture
is diluted in water and the products are extracted with
diethyl ether (three portions of 25 mL). The combined
ethereal extracts are washed with a saturated solution of
sodium hydrogenocarbonate and brine, dried over MgSO4.
The products are isolated using the procedure described in
method a.
4.3.4. 7,7-Diphenylbicyclo[4.1.0] heptan-2-one 4 (new
compound). (C19H18O); MW: 262.352; Anal. calcd for
C19H18O: C, 86.98; H, 6.91; O, 6.10. Found: C, 87.15; H,
7.13; O, 6.21. Pentane/ether: (98/2)–(95/5); obtained:
1
2.10 g (yield: 80%, method a); mp: 94–958C. H NMR
(200 MHz, CDCl3) d 7.60–7.20 (Ph, 10H, m), 2.70–2.10
(3H, m), 1.90–1.60 (5H, m). 13C NMR (50 MHz, CDCl3) d
CO: 209.0; C(Ph): 146.6, 139.0, 130.5, 129.1, 128.6, 127.4,
127.2, 126.5; C-7: 43.9; C-3: 39.3; C-1: 37.4; C-6: 29.0;
C-4, C-5: 22.1, 20.1. EI-MS m/z 262, 244, 234, 219, 218,
208, 206 (base peak), 205, 204, 203, 192, 191, 189, 178,
165, 128, 92, 91. IR n (cm21) (CHCl3) 1678, 1600, 1580,
1495.
4.3.5. 6,6-Diphenylbicyclo[3.1.0]hexan-2-one 5. (C18H16O);
MW: 248.325; CAS RN: 22524-16-9. Pentane/ether:
(95/5)–(85/15); obtained: 2.01 g (yield: 81%, method a);
mp: 108–1098C. 1H NMR9 (200 MHz, CDCl3) d 7.32–7.00
(Ph, 10H, m), 2.67 (cyclopropyl, 1H, pseudo t, J¼5.7 Hz),
2.47 (cyclopropyl, 1H, d, J¼5.7 Hz), 2.30–1.70 (methyl-
ene, 3H, m), 0.87 (methylene, 1H, dt, J¼8.7, 19.3 Hz). 13C
NMR (50 MHz, CDCl3) d CO: 214.0; C(Ph): 144.2, 137.5,
129.9, 128.9, 128.3, 127.2, 126.7, 126.3; C-1: 43.6; C-6:
42.5; C-5: 35.4; C-3: 35.3; C-4: 21.4. EI-MS9 m/z 248, 220,
219, 207, 206 (base peak), 205, 204, 203, 202, 192, 191,
190, 189, 178, 165, 129, 128, 115, 91. IR9 n (cm21) (CHCl3)
1716, 1600, 1495, 1430.
4.3. Isolated products
4.3.1. trans-1-Benzoyl-2,2,3-triphenylcyclopropane 1.
(C28H22O); MW: 374.483; CAS RN: 10266-31-6. Pentane/
ether: (99/1)–(90/10); obtained: 1.55 g (yield: 41%, method
1
a); mp: 125–1268C; H NMR4 (200 MHz, CDCl3) d 8.25
(Hortho, 1H, d, J¼1.3 Hz), 8.20 (Hortho, 1H, d, J¼1.8 Hz),
7.75–7.10 (Ph, 18H, m), 4.25 (H-3, 1H, d, J¼6.2 Hz), 4.20
(H-1, 1H, d, J¼6.2 Hz), for the couple H-3/H-1 (Dn/J¼
1.6 Hz AB system). 13C NMR (50 MHz, CDCl3) d: CO:
195.0; C(Ph): 141.0, 140.5, 138.5, 136.4, 132.7, 129.4,
129.3, 128.5, 128.1, 128.0, 127.9, 127.7, 126.7, 126.4,
126.1; C-2: 51.7; C-1, C-3: 36.7, 36.1. EI-MS m/z: 374, 270,
4.3.6. 8,8-Diphenylbicyclo[5.1.0]octan-2-one 6 (new com-
pound). (C20H20O); MW: 276.379. Anal. calcd for
C20H20O: C, 86.92; H, 7.29; O, 5.79. Found: C, 86.59; H,
7.34; O, 5.63. Pentane/ether: (100/0)–(80/20); obtained:

1080
S. Oudeyer et al. / Tetrahedron 59 (2003) 1073–1081
1.4 g (yield: 51%, method a); mp: 67–688C. 1H NMR
(200 MHz, CDCl3) d 7.45–7.10 (Ph, 10H, m), 2.45–1.15
(Haliphatic, 10H, m). 13C NMR (50 MHz, CDCl3) d CO:
209.3; C(Ph): 146.9, 138.2, 131.1, 128.3, 127.3, 126.8,
126.2; C-8: 43.7; C-3: 41.6; C-1: 41.0; C-7: 28.8; C-4, C-5,
C-6: 24.8, 24.7, 21.8. EI-MS m/z 276, 258, 248, 232, 219,
217, 207, 206, 205 (base peak), 204, 203, 202, 193, 192,
191, 190, 189, 180, 179, 178, 170, 167, 166, 165, 152, 141,
129, 128, 115, 91. IR n (cm21) (CHCl3) 1700, 1665, 1600,
1500, 1430.
NMR11 (200 MHz, CDCl3) d 7.96–7.04 (Ph, 20H, m). 13C
NMR11 (50 MHz, CDCl3) d C(Ph): 141.9, 140.6, 139.8,
139.1, 137.9, 137.1, 133.1, 131.6, 131.0, 130.2, 129.4,
129.3, 128.3, 127.9, 127.6, 127.3, 126.8, 126.2, 126.1.
EI-MS m/z 356 (base peak), 355, 339, 279, 278, 277, 276,
170, 169. IR11 n (cm21) (CCl4) 3060, 3020, 1600.
4.3.11. 5,5-Diphenylpent-4-en-2-one 10. (C17H16O); MW:
236.314; CAS RN: 55004-95-0. Pentane/ether: (100/0)–
(80/20); obtained: 0.128 g (yield: 51%, method b); mp: 50–
518C. 1H NMR12b (200 MHz, CDCl3) d 7.30–7.01 (Ph,
10H, m), 6.16 (H-4, 1H, t, J¼7.3 Hz), 3.11 (H-3, 2H, d, J¼
7.3 Hz), 1.95 (CH3, 3H, s). 13C NMR12b (50 MHz, CDCl3) d
CO: 206.5; C(Ph), Csp2: 144.7, 141.8, 139.4, 129.6, 128.3,
128.1, 127.3, 126.5; C-4: 120.5; C-3: 44.5; C-1: 29.7.
EI-MS12b m/z 236, 194, 193 (base peak), 179, 178, 116, 115.
IR n (cm21) (CH2Cl2) 3040, 2980, 1710, 1660, 1590, 1540,
1490, 1430, 1350.
4.3.7. 3-Methyl-2,2-diphenylcyclopropane-1-carboxalde-
hyde 7a cis/trans, (new compounds). (C17H16O); MW:
236.314. Anal. Calcd for C17H16O: C, 86.40; H, 6.83; O,
6.77. Found: C, 86.27; H, 6.69; O, 6.52.
7a cis/trans: flash chromatography pentane/CH2Cl2:
(80/20)–(0/100); obtained: 0.80 g (yield: 34%, method a);
mixture of cis/trans 55/45 crystallised. 1H NMR (200 MHz,
CDCl3) d cis, [trans] 9.07 (CHO, 1H, d, J¼6.9 Hz), [8.52
(CHO, 1H, d, J¼6.9 Hz)], 7.72–6.99 (Ph, 20H (cis/trans),
m), 2.30–2.11 (H-1, H-3, [H-1], 3H, m), [2.55–2.43 (H-3,
1H, m (d after homodecoupling of methyl at 0.95 ppm,
J¼5.1 Hz)], 1.36 (CH3, 3H, d, J¼6.4 Hz), [0.95 (CH3, 3H,
d, J¼6.3 Hz)]. 13C NMR (50 MHz, CDCl3) d mixture of
cis/trans 55/45 d cis, [trans] CO: 201.3, [200.7]; C(Ph):
145.6, 141.3, 140.3, 136.6, 131.0, 129.1, 129.0, 128.6,
128.3, 127.1, 126.8, 126.5; C-2: 45.8, [46.4]; C-1, C-3,
CH3, 39.8, 28.5, 12.0, [41.9, 25.0, 14.2];. EI-MS m/z cis
236, 221, 208, 207, 206, 205, 192, 191, 189, 179, 178,
166, 165, 130, 129 (base peak), 128, 115, 91, trans 236,
221, 208, 207, 206, 205, 192, 191, 189, 179, 178, 165, 130,
129 (base peak), 128, 115, 91. IR n (cm21) (CCl4/CHCl3)
3060, 3020, 2960, 2940, 2870, 2770, 1705, 1690, 1600,
1580.
4.3.12. 1-Methyl-4-phenylnaphthalene 11. (C17H14), MW:
218.299; CAS RN: 13280-69-8. Pentane: 100; obtained:
1
0.138 g (yield: 60%, method b); mp: 37–388C. H NMR14
(200 MHz, CDCl3) d 8.40–8.26 (Ph, 2H, m), 7.88–7.62
(Ph, 9H, m), 3.05 (CH3, 3H, s). 13C NMR (50 MHz, CDCl3)
d C(Ph): 141.1, 138.8, 133.8, 132.9, 131.8, 130.3, 128.3,
127.1, 126.7, 126.3, 125.7, 124.5; CH3: 19.7. EI-MS m/z
218 (base peak), 217, 215, 204, 203, 202, 189, 165, 115,
107, 101, 95. IR n (cm21) (CHCl3) 3080, 3050, 2990, 2940,
2880, 1600, 1520.
4.3.13. 4,5,5-Triphenylpent-4-en-2-one 12. (C23H20O);
MW: 312.412; CAS RN: 7593-09-1. Not isolated. EI-MS
m/z 312, 270, 269, 192, 191 (base peak), 190, 189, 178, 165,
91.
4.3.14. 4-Methyl-1,2-diphenylnaphthalene 13 (new com-
pound). (C23H18); MW: 294.397; HR-MS calcd for C23H18
(M)þ m/z 294.1408, found: 294.1407. Pentane: (100);
obtained: 0.17 (yield: 72%, method b); mp: 139–1408C.
1H NMR (200 MHz, CDCl3) d 8.37 (Ph, 1H, d, J¼8.2 Hz),
8.08 (Ph, 1H, d, J¼8.2 Hz), 7.85–7.45 (Ph, 13H, m), 3.07
(CH3, 3H, s). 13C NMR (50 MHz, CDCl3) d C(Ph): 142.1,
139.3, 138.0, 136.0, 133.7, 132.9, 131.9, 131.6, 130.1,
129.2, 129.0, 127.8, 127.6, 126.6, 126.1, 125.9, 125.6,
124.1; CH3: 19.5. EI-MS m/z 294 (base peak), 280, 279,
278, 277, 276, 215, 138, 132. IR n (cm21) (CHCl3) 3060,
2990, 1640, 1600, 1560.
4.3.8. 1,1-Diphenyl-2-(prop-1-enyl)oxirane 7b. (C17H16O);
MW: 236.314. Characterized by 1H NMR, 13C NMR, EI-Ms
but not isolated (purity: 88%). Flash chromatography
Pentane/CH2Cl2: (80/20); obtained: 0.29 g (yield: 12%,
method a); oil. 1H NMR (200 MHz, CDCl3) 7.34–7.10 (Ph,
10H, m), 5.87 (H-20, 1H, dq, J¼15.5, 6.6 Hz), 4.83 (H-10,
1H, ddq, J¼15.5, 8.8, 1.5 Hz), 3.64 (H-2, 1H, d, J¼8.8 Hz),
1.54 (CH3, 3H, dd, J¼6.6, 1.5 Hz). 13C NMR (50 MHz,
CDCl3) d C(Ph), Csp2: 141.0, 137.4, 133.5, 128.3, 128.1,
127.7, 126.7; C-1, C-2: 67.1; CH3: 18.0. EI-MS m/z: 236,
235, 207, 167, 166, 165 (base peak), 164, 129, 105.
4.3.9. 1,3,4,4-Tetraphenylbut-3-en-1-one 8. (C28H22O);
MW: 374.483; CAS RN: 53449-11-9. Pentane/ether:
(99/1)–(90/10); obtained: 0.202 g (yield: 81%, method b);
4.3.15. 3-Methyl-4,4-diphenylbut-3-enal 14. (C17H16O);
MW: 236.314. Not isolated. EI-MS m/z 209, 208, 207, 194,
193, 192, 191, 190, 189, 179, 178, 166, 165, 164, 152, 131,
130 (base peak), 129, 115, 91.
1
mp: 195–1968C. H NMR10 (200 MHz, CDCl3) d 7.97–
7.08 (Ph, 20H, m), 4.37 (H-2, 2H, s). 13C NMR10 (50 MHz,
CDCl3) d CO: 197.8; C(Ph), Csp2: 143.3, 143.0, 142.4,
142.3, 137.0, 133.3, 132.9, 130.7, 129.7, 129.2, 128.5,
128.4, 128.0, 127.9, 127.5, 127.1, 126.4, 126.2; C-2: 46.4.
EI-MS10 m/z 374, 270, 269 (base peak), 192, 191, 189, 165,
105, 91, 77; IR n (cm21) (CCl4) 3060, 3020, 1690, 1440,
1410, 1330.
4.3.16. 2-Methyl-1-phenylnaphthalene 15. (C17H14), MW:
218.299; CAS RN: 29304-63-0. Pentane: (100); obtained:
0.076 g (yield: 33%, method b); mp: 43–448C. 1H NMR16b
(200 MHz, CDCl3) d 7.75–7.65 (Ph, 2H, m), 7.44–7.10
(Ph, 9H, m), 2.14 (CH3, 3H, s). 13C NMR16b (50 MHz,
CDCl3) d C(Ph): 139.8, 138.2, 133.1, 133.0, 131.0, 130.2,
128.6, 128.4, 127.7, 127.2, 127.0, 126.2, 125.8, 124.7; CH3:
20.8. EI-MS m/z 218 (base peak), 217, 215, 204, 203, 202,
189, 115, 108, 101, 95. IR16a n (cm21) (CHCl3) 3080, 2990,
2940, 1600, 1520.
4.3.10. 1,2,4-Triphenylnaphthalene 9. (C28H20); MW:
356.468; CAS RN: 806-58-6. Pentane: (100); obtained:
0.048 g (yield: 20%, method b); mp: 158–1608C. 1H

S. Oudeyer et al. / Tetrahedron 59 (2003) 1073–1081
1081
4.3.17. 3-Benzhydrylidenecyclohexanone 16. (C19H18O),
MW: 262.352. Not isolated. EI-MS m/z 262, 203, 184, 183
(base peak), 106, 105, 77.
C-8: 61.0; C-4, C-7: 41.8, 42.8; C-5, C-6: 25.2, 21.1. EI-MS
m/z 276, 258, 234, 233, 206, 205, 204, 193, 192, 191, 190,
185, 180, 179, 178, 168, 167 (base peak), 166, 165, 153,
152, 129, 115, 109, 91, 81, 79. IR n (cm21) (CHCl3) 1660,
1600, 1450.
4.3.18. 3-Benzhydrylcyclohex-2-en-1-one 17. (C19H18O),
MW: 262.352; CAS RN: 21086-47-5. Pentane/ether:
(95/5)–(85/15); obtained: 0.168 g (yield: 67%, method b);
1
oil. H NMR17 (200 MHz, CDCl3) d 7.24–7.00 (Ph, 10H,
m), 5.57 (H-2, 1H, s), 4.78 (H-7, 1H, s), 2.32–2.18 (CH2,
4H, m), 1.92–1.79 (CH2, 2H, m). 13C NMR (50 MHz,
CDCl3) d CO: 199.7; C-3: 167.1; C(Ph), C-2: 140.1, 129.1,
128.6, 127.0; C-7: 59.0; C-4, C-6: 37.5, 30.1; C-5: 22.9.
EI-MS m/z 262, 247, 244, 234, 233, 219, 218, 217, 215, 207,
206 (base peak), 205, 204, 203, 202, 192, 191, 190, 189,
179, 178, 171, 168, 167, 166, 165, 164, 152, 130, 129, 128,
115, 91. IR17 n (cm21) (CCl4) 3080, 3060, 3020, 2940,
2860, 1680, 1620, 1490, 1450, 1430, 1360, 1340, 1320.
References
´ ´ ´
1. (a) Leonel, E.; Paugam, J. P.; Condon-Gueugnot, S.; Nedelec,
J.-Y. Tetrahedron 1998, 54, 3207–3218. (b) Sengmany, S.;
´
Leonel, E.; Paugam, J. P.; Nedelec, J.-Y. Tetrahedron 2002,
´ ´
´
58, 271–277. (c) Sengmany, S.; Leonel, E.; Paugam, J. P.;
´ ´
Nedelec, J.-Y. Synthesis 2002, 533–537.
2. (a) Julia, M.; Julia, S.; Tchen, S. Y. Bull. Soc. Chim. Fr. 1961,
1849–1853. (b) Wenkert, E.; Mueller, R. A.; Reardon, Jr. E. J.;
Sathe, S. S.; Scharf, D. J.; Tosi, G. J. Am. Chem. Soc. 1970, 92,
7428–7436. (c) Tenney, L. P.; Boykin, D. W.; Lutz, R. E.
J. Am. Chem. Soc. 1966, 88, 1835–1836.
4.3.19. 3-Benzhydrylidenecyclopentanone 18. (C18H16O);
MW: 248.325. Not isolated. EI-MS m/z 248 (base peak),
220, 219, 206, 205, 204, 203, 202, 192, 191, 190, 189, 178,
167, 166, 165, 129, 128, 115, 91.
3. (a) Staudinger, H.; Anthes, E.; Pfenninger, F. Ber. 1916, 49,
1928–1941. (b) Van Alphen, J. Rec. Trav. Chim. Pays Bas
1943, 62, 210–214.
4.3.20. 3-Benzhydrylcyclopent-2-en-1-one 19. (C18H16O);
MW: 248.325; CAS RN: 70239-00-8. Pentane/ether:
(95/5)–(85/15); obtained: 0.145 g (yield: 58%, method b);
¨
4. Weber, E.; Hecker, M.; Csoregh, I.; Czugler, M. J. Am. Chem.
Soc. 1989, 111, 7866–7872.
5. Nishida, S.; Fujioka, T.; Shimizu, N. J. Organometal. Chem.
1978, 156, 37–44.
1
mp: 68–698C. H NMR18 (200 MHz, CDCl3) d 7.28–7.06
(Ph, 10H, m), 5.71 (H-2, 1H, s), 4.92 (H-6, 1H, s), 2.53–
2.50 (CH2, 2H, m), 2.39–2.35 (CH2, 2H, m). 13C NMR
(50 MHz, CDCl3) d CO: 209.5; C-3: 183.4; C(Ph): 140.5;
C-2: 132.7; C(Ph): 128.2, 127.3; C-6: 55.9; C-4, C-5: 35.7,
31.2. EI-MS m/z 248, 220, 219, 207, 206 (base peak), 205,
204, 203, 194, 192, 191, 190, 189, 167, 166, 165, 152, 142,
141, 129, 128, 115, 91. IR18 n (cm21) (CCl4) 3080, 3060,
3030, 2920, 2860, 1710, 1600, 1490, 1450, 1440, 1410.
6. Walborsky, H. M.; Hornyak, F. M. J. Am. Chem. Soc. 1955,
77, 6026–6029.
7. Impastato, J. F.; Walborsky, H. M. J. Am. Chem. Soc. 1962,
84, 4838–4843.
8. Gan, C. Y.; Lambert, J. N. J. Chem. Soc., Perkin Trans. 1
1998, 15, 2363–2372.
9. Zimmerman, H. E.; Diehl, D. R. J. Am. Chem. Soc. 1979, 101,
1841–1857.
10. Santiago, A. N.; Lassaga, G.; Rappoport, Z.; Rossi, R. A.
J. Org. Chem. 1996, 61, 1125–1128.
4.3.21. 3-Benzhydrylidenecycloheptanone 20 (new com-
pound). (C20H20O); MW: 276.379. Anal. calcd for
C20H20O: C, 86.92; H, 7.29; O, 5.79. Found: C, 86.79; H,
7.19; O, 5.44. Pentane/ether: (90/10); obtained: 0.152 g
(yield: 61%, method b); mp: 74–758C. 1H NMR (200 MHz,
CDCl3) d 7.25–7.00 (Ph, 10H, m), 3.20 (H-2, 2H, s), 2.55–
2.50 (CH2, 2H, m), 2.25–2.20 (CH2, 2H, m), 1.75–1.55
(CH2, 4H, m). 13C NMR (50 MHz, CDCl3) d CO: 211.9;
C(Ph), Csp2: 142.1, 141.7, 131.7, 128.6, 128.1, 126.6,
126.4; C-2: 49.8; C-7: 43.7; C-4, C-5, C-6: 34.5, 30.1, 24.7.
EI-MS m/z 276 (base peak), 220, 219, 218, 206, 205, 203,
194, 192, 191, 190, 189, 180, 179, 178, 167, 166, 165, 129,
115, 91. IR n (cm21) (CHCl3) 1698, 1599, 1500, 1430.
11. Larock, R. C.; Tian, Q. J. Org. Chem. 1998, 63, 2002–2009.
12. (a) Tschesche, J. R.; Machleidt, H. J. Liebigs Ann. Chem.
1960, 631, 61–76. (b) Katritzky, A. R.; Li, J.; Gordeev, M. F.
J. Org. Chem. 1993, 58, 3038–3041.
13. Blomquist, A. T.; Bottomley, C. G. J. Liebigs Ann. Chem.
1962, 653, 67–79.
14. Eustathopoulos, H.; Rinaudo, J.; Bonnier, J. M. Bull. Soc.
chim. Fr. 1973, 2384–2388.
15. Harris, T. M.; Harris, C. M. J. Org. Chem. 1967, 32, 970–975.
16. (a) Bonnier, J. M.; Rinaudo, J. Bull. Soc. Chim. Fr. 1970,
146–150. (b) Alt, H. G.; Zenk, R.; Milius, W. J. Organomet.
Chem. 1996, 514, 257–270.
17. Kawanisi, M.; Kamogawa, K.; Okada, T.; Norzaki, H.
Tetrahedron 1968, 24, 6557–6562.
4.3.22. 3-Benzhydrylcyclohept-2-en-1-one 21 (new com-
pound). (C20H20O); MW: 276.379. FAB-HR-MS calcd for
C20H21O (MþH)þ m/z 277.1592, found 277.1586. Pentane/
ether: (90/10); obtained: 0.06 g (yield: 24%, method b); mp:
18. Zimmerman, H. E.; Zhu, Z. J. Am. Chem. Soc. 1995, 117,
5245–5262.
1
19. Quillet, J. P.; Dreux, J. Bull. Soc. Chim. Fr. 1966, 645–652.
20. Bonnier, J. M.; Rinaudo, J.; Bouvier, C. Bull. Soc. Chim. Fr.
1967, 4067–4069.
91–928C. H NMR (200 MHz, CDCl3) d 7.25–7.00 (Ph,
10H, m), 5.60 (H-2, 1H, s), 4.80 (H-8, 1H, s), 2.50–2.45
(CH2, 2H, m), 2.35–2.30 (CH2, 2H, m), 1.85–1.55 (CH2,
4H, m). 13C NMR (50 MHz, CDCl3) d CO: 204.3; C-3:
162.7; C(Ph): 140.5; C-2: 132.2; C(Ph): 129.3, 128.6, 127.0;
21. Tournier, H.; Longeray, R.; Dreux, J. Bull. Soc. Chim. Fr.
1972, 3214–3221.