Copper catalyzed conjugate addition of highly functionalized arylmagnesium compounds to enones

Article abstract of DOI:10.1016/S0040-4020(00)00127-7

Highly functionalized arylmagnesium bromides are readily prepared by an iodine-magnesium exchange reaction. In the presence of catalytic amounts of copper(I) salts and chlorotrimethylsilane, they add to various enones leading to the conjugate addition pro

Full text of DOI:10.1016/S0040-4020(00)00127-7

TETRAHEDRON
Pergamon
Tetrahedron 56 (2000) 2727±2731
Copper Catalyzed Conjugate Addition of Highly Functionalized
Arylmagnesium Compounds to Enones
a,b
Greta Varchi, Alfredo Ricci, Gerard Cahiez and Paul Knochel
b
c
a,
*
Â
a
È
È
È
È
Institut fur Organische Chemie, Ludwig Maximilians Universitat Munchen, Butenandtstr. 5-13, D-81377 Munchen, Germany
bDipartimento di Chimica Organica `A. Mangini' Universita degli Studi di Bologna, Sede Viale Risorgimento, 4, I-40136 Bologna, Italy
 Â
Ecole Superieure de Chimie Organique et Minerale (ESCOM), Department of Organic Chemistry and NMR, 13, boulevard de l'Hautil,
F-95092 Cergy-Pontoise, France
c
Received 12 April 1999; revised 30 November 1999; accepted 14 December 1999
AbstractÐHighly functionalized arylmagnesium bromides are readily prepared by an iodine±magnesium exchange reaction. In the
presence of catalytic amounts of copper(I) salts and chlorotrimethylsilane, they add to various enones leading to the conjugate addition
products in 66±89% yield. q 2000 Elsevier Science Ltd. All rights reserved.
The scope of the applications of organometallic reagents to
organic synthesis strongly depends on the availability of
highly functionalized carbon groups attached to the metal.
Numerous functionalized organozinc compounds have been
successfully prepared and used in synthesis.1 Only recently
an ef®cient iodine±magnesium exchange reaction has
allowed the preparation of highly functionalized aryl-
magnesium compounds.2,3 These reagents led to interesting
applications in solution2±5 and in solid phase synthesis.2,3
Herein, we wish to report the generation of highly func-
tionalized organomagnesium reagents and their conjugate
addition to various enones. The presence of chlorotrimethyl-
silane proved to be essential for the success of the
reaction.6±10 Thus, the reaction of ethyl 3-iodobenzoate
(1a, 1.05 equiv.) with i-PrMgBr (1.20 equiv.) in THF at
2408C for 1 h produces the expected functionalized aryl-
magnesium compound 2a as indicated by gas chromato-
graphical analysis of reaction mixture aliquots quenched
with sat. NH4Cl solution or iodine. To this organometallic,
a mixture of cyclohexenone (1.0 equiv.), CuI (0.1 equiv.),
LiCl (0.2 equiv.)11 and Me3SiCl (1.0 equiv.) was added at
2408C (Method A).10 After 1 h, the conversion was
complete and the desired 1,4-adduct (3a) was isolated in
74% yield (see entry 1 of Table 1 and Scheme 1).
the iodine±magnesium exchange reaction allows a low
temperature preparation of arylmagnesium derivatives
bearing an ester, an amide or a nitrile function. All these
organometallics undergo a smooth 1,4-addition to various
polyfunctional enones. Extensions of this methodology to
more complex organomagnesium reagents is underway.
Experimental
General methods
THF and HMPA were dried over sodium and CaH2, respec-
tively, and distilled prior to use. Commercially available
starting materials were used without further puri®cation.
Typical procedures
Preparation of 3-(3-carbethoxyphenyl)cyclohexanone
(3a). Method A. A three-necked ¯ash equipped with a
septum, a glass stopper and an argon inlet was charged
with dry LiCl (dried 1 h at 1308C at 0.1 mmHg; 16.2 mg,
0.384 mmol), CuI (36.6 mg, 0.192 mmol) and THF (6 mL).
To the resulting solution, Me3SiCl (0.25 mL, 1.92 mmol)
and 2-cyclohexenone (185 mg, 1.92 mmol) was added. A
second three-necked ¯ask equipped with a septum, a
thermometer and an argon inlet was charged with ethyl
3-iodobenzoate (1a: 566 mg, 2.0 mmol) in THF (1.5 mL)
and was cooled to 2408C. i-PrMgBr (2.5 mL, 2.3 mmol
of a 0.87 M solution in THF) was slowly added and the
reaction mixture was stirred for 1 h at this temperature.
The solution of the ®rst ¯ask was added and the resulting
solution was stirred for 1 h and was quenched with a sat.
solution of aq. NH4Cl. The aqueous phase was extracted
several times with ether and the combined organic phase
Under these conditions, typical cyclic and acyclic enones
provide the desired products in satisfactory yields. Alterna-
tively, CuBr´Me2S (5 mol%), Me3SiCl (2 equiv.) in a
THF:HMPA mixture (Method B) gives excellent results as
well (see entries 2, 6±9 and 5±6 of Table 1). In summary,
Keywords: copper catalysis; conjugate addition; polyfunctional organo-
magnesium compounds.
* Corresponding author. Tel.: 149-89-2180-7681; fax: 149-89-2180-
7680; e-mail: paul.knochel@cup.uni-muenchen.de
0040±4020/00/$ - see front matter q 2000 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020(00)00127-7

2728
G. Varchi et al. / Tetrahedron 56 (2000) 2727±2731
Table 1. Conjugate addition products 3a±p obtained by the copper(I) catalyzed addition of polyfunctional organomagnesium compounds to enones in the
presence of TMSCl
Entry
Substrate of type 1
Method
Enone 2
Product of type 3
Yielda (%)
1
Method A
74
1a
2
3
1a
1a
Method B
Method A
72
74
4
1a
Method A
80
5
6
1a
Method A
Method B
68
73
1b
1b
7
8
Method B
Method B
75
69
1b
1b
9
Method B
Method A
74
89
10
1c
1c
11
Method A
73

G. Varchi et al. / Tetrahedron 56 (2000) 2727±2731
2729
Table 1 (continued)
Entry
Substrate of type 1
Method
Enone 2
Product of type 3
Yielda (%)
12
1c
1a
Method A
Method A
69
13
14
15
67
72
66
Method A
Method B
1d
1d
16
1d
Method B
68
17
1d
Method A
70
a Isolated yield of analytically pure product.
was dried (MgSO4) and the solvent was evaporated. The
crude residue was puri®ed by ¯ash-chromatography (ether:
pentane 1:5) affording the desired ketone 3a (349 mg, 74%
yield) as a yellowish oil.
After 1 h reaction time, the reaction mixture was worked up
as described above and the crude residue was puri®ed by
¯ash-chromatography (ether:pentane 1:5) affording the
desired product 3a (177 mg, 72% yield) as a yellowish oil.
Method B. A three-necked ¯ask equipped with a septum, a
glass stopper and an argon inlet was charged with
CuBr´Me2S (10.3 mg, 0.05 mmol), Me3SiCl (0.26 mL,
2 mmol) and 2-cyclohexenone (96 mg, 1 mmol) in HMPA
(0.35 mL, 2 mmol). This solution was added at 2408C to a
three-necked ¯ask containing 3-carbethoxyphenylmagne-
sium bromide prepared from ethyl 3-iodobenzoate (1a;
389 mg, 1.4 mmol) and i-PrMgBr (1.66 mL, 1.61 mmol of
a 0.97 M solution in THF) prepared according to method A.
Analytical data of compounds (3a±p) of Table 1
3-(3-Carbethoxyphenyl)cyclohexanone (3a). 1H NMR
(300 MHz, CDCl3): d 1.42 (3H, t, Jˆ7.1 Hz, CH3), 1.64±
1.89 (2H, m, CH2), 2.02±2.11 (2H, m, CH2), 2.30±2.48 (2H,
m, CH2), 2.49±2.62 (2H, m, CH2), 2.98±3.14 (1H, m, CH),
4.35 (2H, q, Jˆ7.1 Hz, CH2). 7.36±7.45 (2H, m, ArH),
7.88±7.97 (2H, m, ArH). 13C NMR (75 MHz, CDCl3):
14.1 (CH3), 25.2 (CH2), 32.3 (CH2), 40.7 (CH2), 44.2
Scheme 1.

2730
G. Varchi et al. / Tetrahedron 56 (2000) 2727±2731
(CH), 48.4 (CH2), 60.7 (OCH2), 127.4, 127.6, 128.4
(ArCH), 130.9 (ArC), 130.9 (ArCH), 144.5 (ArC), 166.1
(COOEt), 209.7 (CO). MS (EI): 246 (M1), 200
(M12EtO), 131, 103. IR: (CHCl3): 3514±2252
(ArCH),1720 (CO, COOEt); (cm21). Anal. Calcd For
C15H18O3: C 73.15, H 7.37. Found: C 73.20, H 7.32
m, CH2), 4.24±4.31 (1H, m, CH), 4.37 (2H, q, Jˆ7.1 Hz,
CH2), 7.28±7.46 (3H, m, ArH), 7.85 (1H, dd, Jˆ7.8 and
1.4 Hz, ArH). 13C NMR (75 MHz, CDCl3): 14.1 (CH3),
30.8 (CH2), 38.3 (CH), 38.5 (CH2), 45.7 (CH), 60.9
(OCH2), 126.0, 126.2, 130.3 (ArCH), 130.5 (ArC), 131.9
(ArCH), 143.7 (ArC), 167.6 (COOEt), 218.0 (CO). MS
(EI): 232 (M1), 186 (M12EtO), 133, 105. IR: (CHCl3):
3530±2270 (ArCH),1715 (CO, COOEt); (cm21). Anal.
Calcd For C14H16O3: C 72.39, H 6.07. Found: C 72.54, H
5.92.
3(3-Carbethoxyphenyl)cyclopentanone (3b). 1H NMR
(300 MHz, CDCl3): d 1.40 (3H, t, Jˆ7.2 Hz, CH3), 1.93±
2.31 (1H, m, CH2), 2.24±2.54 (4H, m, CH2), 2.62±2.76 (1H,
m, CH2), 3.40±3.55 (1H, m, CH2), 4.38 (2H, q, Jˆ7.1 Hz,
CH2). 7.36±7.45 (2H, m, ArH), 7.88±7.97 (2H, m, ArH).
13C NMR (75 MHz, CDCl3): 14.2 (CH3), 31.0 (CH2),
38.7 (CH), 41.9 (CH2), 45.5 (CH2), 60.9 (OCH2), 127.7,
127.8, 127.9 (ArCH), 130.8 (ArC), 131.1 (ArCH), 143.3
(ArC), 166.3 (COOEt), 217.4 (CO). MS (EI): 232 (M1),
186 (M12EtO), 131, 103. IR: (CHCl3): 3522±2263
(ArCH),1725 (CO, COOEt); (cm21). Anal. Calcd For
C14H16O3: C 72.39, H 6.07. Found: C 72.12, H 6.34
Ethyl 2-(1,3-diphenyl-3-oxopropyl)benzoate (3g). 1H
NMR (300 MHz, CDCl3): d 1.37 (3H, t, Jˆ7.1 Hz, CH3),
3.73 (2H, d, Jˆ5.6 Hz CH2), 4.35 (2H, q, Jˆ7.1 Hz, CH2),
4.91 (1H, t, Jˆ5.6 Hz CH), 7.16±7.52 (10H, m, ArH), 7.87±
7.99 (4H, m, ArH). 13C NMR (75 MHz, CDCl3): 14.2 (CH3),
41.1 (CH), 44.8 (CH2), 61.1 (OCH2), 126.0, 126.2, 127.6,
127.8, 128.0, 128.3, 128.5, 128.6, (ArCH), 130.1 (ArC),
131.5, 132.9 (ArCH), 136.9, 143.5, 144.8 (ArC), 167.9
(COOEt), 197.5 (CO). MS (EI): 358 (M1),
312(M12EtO),225, 207 (312-COPh), 197. IR: (CHCl3):
2895±3000 (ArCH), 1730 (CO2Et), 1700 (CO); (cm21).
Anal. Calcd For C24H22O3: C 80.42, H 6.19. Found: C
80.63, H 5.98
Ethyl 3-(1,3-diphenyl-3-oxopropyl)benzoate (3c). 1H
NMR (300 MHz, CDCl3): d 1.34 (3H, t, Jˆ7.1 Hz, CH3),
3.76 (2H, d, Jˆ5.5 Hz CH2), 4.3 (2H, q, Jˆ7.1 Hz, CH2),
4.88 (1H, t, Jˆ5.6 Hz, CH), 7.12±7.49 (10H, m, ArH),
7.90±7.98 (4H, m, ArH). 13C NMR (75 MHz, CDCl3):
14.5 (CH3), 44.7 (CH2), 46.0 (CH), 61.1 (OCH2), 126.8,
127.8, 128.0, 128.2, 128.8, 128.8, 128.9, 129.8 (ArCH),
131.0 (ArC), 132.8, 133.3 (ArCH), 137.2, 143.9, 144.7
(ArC), 166.7 (COOEt), 197.8 (CO). MS (EI): 358 (M1),
312(M12EtO), 207 (312-COPh), 165, 105. IR: (CHCl3):
2890±3010 (ArCH), 1790 (CO2Et), 1705 (CO); (cm21).
Anal. Calcd For C24H22O3: C 80.42, H 6.19. Found: C
80.63, H 5.98
1
Ethyl 2-(3-oxobutyl)benzoate (3h). H NMR (300 MHz,
CDCl3): d 1.29 (3H, t, Jˆ7.1 Hz, CH3), 2.05 (3H, s, CH3),
2.68 (2H, t, Jˆ5.0 Hz, CH2), 5.01 (2H, t, Jˆ7.1 Hz, CH2),
4.26 (2H, q, Jˆ7.1 Hz, CH2), 7.14±7.19 (2H, m, ArH),
7.30±7.35 (1H, m, ArH), 7.81 (1H, dd, Jˆ7.3 and 1.5 Hz,
ArH). 13C NMR (75 MHz, CDCl3): 14.2 (CH3), 27.2 (CH3),
28.8 (CH2), 29.7 (CH2), 45.3 (CH), 60.8 (CH2), 126.5,
130.7, 131.1, 132.0 (ArCH), 134.0, 142.8 (ArC), 167.3
(COOEt), 207.8 (CO). MS (EI): 220 (M1), 174
(M12EtO), 147 (M12CO2Et), 131, 91. IR: (CHCl3):
2895±3010 (ArCH), 1735 (CO2Et, CO); (cm21). Anal.
Calcd For C13H16O3: C 70.88, H 7.32. Found: C 70.97, H
7.23.
1
Ethyl 3-(3-oxobutyl)benzoate (3d). H NMR (300 MHz,
CDCl3): d 1.39 (3H, t, Jˆ7.2 Hz, CH3), 2.14 (3H, s, CH3),
2.79 (2H, t, Jˆ7.4 Hz, CH2), 4.36 (2H, q, Jˆ7.1 Hz, CH2),
7.31±7.41 (2H, m, ArH), 7.80±7.90 (2H, m, ArH). 13C
NMR (75 MHz, CDCl3): 14.2 (CH3), 29.3 (CH3), 29.8
(CH2), 44.6 (CH2), 60.8 (CH2), 127.2, 128.3, 129.1, 132.8
(ArCH), 130.6, 141.2 (ArC), 166.4 (COOEt), 207.1 (CO).
MS (EI): 220 (M1), 174 (M12EtO), 147 (M12CO2Et),
131, 91. IR: (CHCl3): 2890±3007 (ArCH), 1750 (CO2Et,
CO); (cm21). Anal. Calcd For C13H16O3: C 70.88, H 7.32.
Found: C 70.63, H 7.58.
N, N-Dibenzyl 4-(3-oxocyclohexyl)benzamide (3i). 1H
NMR (300 MHz, CDCl3): d 1.59±1.65 (2H, m, CH2),
1.86±1.93 (2H, m, CH2), 2.22±2.26 (2H, m,CH2), 2.33±
2.39 (2H, m,CH2), 2.75±2.97 (1H, m, CH), 4.29 (2H,
s,CH2Ph), 4.56 (2H, s,CH2Ph), 6.89±7.88 (12H, m, ArH),
7.35 (2H, d, ArH). 13C NMR (75 MHz, CDCl3): 24.8 (CH2),
32.0 (CH2), 40.5 (CH2), 43.9 (CH), 46.4 (CH2Ph), 48.0
(CH2), 51.1 (CH2Ph), 126.3, 126.4, 126.7 (ArCH), 127.0,
127.8, 127.8, 128.2 (ArCH), 134.0, 135.9, 136.4, 145.5
(ArC), 171.4 (CON(CH2Ph)2), 209.7 (CO). MS (EI): 397
(M1), 306 (M1291), 231 (M12NBn2), 91. IR: (CHCl3):
2890±2990 (ArCH), 1720 (CONBn2), 1640 (CO); (cm21).
Anal. Calcd For C27H27NO2: C 81.58, H 6.85. Found: C
81.71, H 6.72.
Ethyl 2-(3-oxocycloheyl)benzoate (3e). 1H NMR
(300 MHz, CDCl3): d 1.30 (3H, t, Jˆ7.1 Hz, CH3), 1.74±
1.79 (2H, m, CH2), 2.00±2.10 (2H, m, CH2), 2.37±2.51 (4H,
m,CH2), 3.77±3.81 (1H, m, CH), 4.27 (2H, q, Jˆ7.1 Hz,
CH2), 7.20±7.42 (3H, m, ArH), 7.73 (1H, dd, Jˆ8.7 and
1.4 Hz, ArH). 13C NMR (75 MHz, CDCl3): 14.2 (CH3),
25.4 (CH2), 32.7 (CH2), 40.1 (CH), 41.1 (CH2), 48.4
(CH2), 61.0 (CH), 126.2, 126.4 (ArCH), 130.1 (ArC),
130.3, 131.8 (ArCH), 144.8 (ArC), 167.7 (COOEt), 210.6
(CO). MS (EI): 246 (M1), 200 (M12EtO), 172 (200-CO),
144. IR: (CHCl3): 2895±3000 (ArCH),1730 (CO, CO2Et);
(cm21). Anal. Calcd For C15H18O3: C 73.15, H 7.37. Found:
C 73.25, H 7.27.
N, N-Dibenzyl 4(3-oxocyclopentyl)benzamide (3j). 1H
NMR (300 MHz, CDCl3): d 2.17±2.33 (1H, m, CH2),
2.49±2.78 (4H, m, CH2), 2.87±2.99 (1H, m,CH2), 3.61±
3.78 (1H, m, CH), 4.71 (2H, s, CH2Ph), 4.99 (2H,
s,CH2Ph), 7.40±7.68 (12H, m, ArH), 7.79 (2H, d,
Jˆ8.05 Hz, ArH). 13C NMR (75 MHz, CDCl3): 30.8
(CH2), 38.5 (CH2), 41.8 (CH), 45.3 (CH2), 46.8 (CH2Ph),
51.4 (CH2Ph), 126.8, 127.0, 127.4, 127.8, 127.9, 128.2,
128.6 (ArCH), 134.4, 136.3, 136.7, 144.7 (ArC), 171.8
Ethyl 2-(3-oxocyclopentyl)benzoate (3f). 1H NMR
(300 MHz, CDCl3): d 1.39 (3H, t, Jˆ7.0 Hz, CH3), 1.99±
2.32 (1H, m, CH2), 2.33±2.41 (4H, m, CH2), 2.66±2.73 (1H,

G. Varchi et al. / Tetrahedron 56 (2000) 2727±2731
2731
(CON(CH2Ph)2), 217.4 (CO). MS (EI): 383 (M1), 292
(M1291), 187 (M12NBn2), 91. IR: (CHCl3): 2895±3000
(ArCH), 1715 (CONBn2), 1670 (CO); (cm21). Anal. Calcd
For C26H25NO2: C 81.43, H 6.57. Found: C 81.61, H 6.39.
(CH2), 45.6 (CH), 109.9 (CN), 118.2 (ArC), 127.4, 132.7
(ArCH), 148.5 (ArC), 198.7 (CO). MS (EI): 311 (M1), 282
(M1229), 220(M1291), 103, 89. IR: (CHCl3): 2890±2990
(ArCH), 2218 (CN), 1689 (CO); (cm21). Anal. Calcd For
C22H17NO: C 84.86, H 5.50. Found: C 84.74, H 5.62.
N, N-Dibenzyl 4-(1,3-diphenyl-3-oxopropyl)benzamide
(3k). 1H NMR (200 MHz, CDCl3): d 3.71 (2H, d,
Jˆ7.4 Hz, CH2), 4.39 (2H, s,CH2Ph), 4.65 (2H, s,CH2Ph),
4.85 (1H, t, Jˆ6.4 Hz, CH), 7.05±7.55 (12H, m, ArH), 7.81
(2H, d, Jˆ8.1 Hz, ArH). 13C NMR (75 MHz, CDCl3): 44.3
(CH2), 45.6 (CH), 46.8 (CH2Ph), 51.5 (CH2Ph), 126.5,
126.6, 126.8, 126.9, 127.1, 127.3, 127.4, 127.7, 127.9,
128.0 (ArCH), 129.6 (ArC), 133.1 (ArCH), 133.9, 136.3,
143.4, 145.9 (ArC), 171.9 (CON(CH2Ph)2), 197.5 (CO).
MS (EI): 509 (M1), 418 (M1291), 313 (M12NBn2),
298, 91. IR: (CHCl3): 2890±3000 (ArCH), 1722
(CONBn2), 1674 (CO); (cm21). Anal. Calcd For
C26H25NO2: C 84.84, H 6.13. Found: C 84.79, H 6.18.
4-(3-Oxobutyl)benzonitrile (3p). 1H NMR (200 MHz,
CDCl3): d 2.12 (3H, s, CH3), 2.75 (2H, dd, Jˆ9.7 and
2.6 Hz, CH2), 2.87 (2H, dd, Jˆ9.7 and 2.6 Hz, CH2), 7.25
(2H, d, ArH), 7.50 (2H, d, ArH). 13C NMR (75 MHz,
CDCl3): 29.3 (CH2), 29.8 (CH3), 43.9 (CH2), 109.6 (CN),
118.7 (ArC), 129.0, 132.0 (ArCH), 146.6 (ArC), 206.6
(CO). MS (EI): 173 (M1), 158 (M1215),
130(M12COMe), 103. IR: (CHCl3): 2890±2990 (ArCH),
2215 (CN), 1720 (CO); (cm21). Anal. Calcd For C11H11NO:
C 76.28, H 6.40. Found: C 76.34, H 6.34.
Acknowledgements
N, N-Dibenzyl 4-(3-oxobutyl)benzamide (3l). 1H NMR
(200 MHz, CDCl3): d 2.12 (3H, s, CH3), 2.75 (2H, dd,
Jˆ10 and 3 Hz, 2CH2), 2.87 (2H, dd, Jˆ10 Hz, Jˆ3 Hz,
2CH2), 4.45 (2H, s, CH2Ph), 4.70 (2H, s, CH2Ph), 7.05±
7.62 (14H, m, ArH). 13C NMR (75 MHz, CDCl3):
29.2(CH2), 29.5 (CH3), 44.6 (CH2), 47.0 (CH2Ph), 51.4
(CH2Ph), 126.9, 127.4, 127.8, 128.0, 128.3 (ArCH) 129.1,
133.7, 142.8 (ArC), 172.1 (CON(CH2Ph)2), 207.3 (CO).
MS (EI): 371 (M1), 280 (M1291), 175 (M12NBz2), 91.
IR: (CHCl3): 2880±2990 (ArCH), 1721 (CONBn2), 1669
(CO); (cm21). Anal. Calcd For C25H25NO2: C 80.83, H
6.78. Found: C 80.91, H 6.70.
We thank the DFG (Leibniz program) and the Fonds der
Chemischen Industrie for generous support. We thank
Degussa AG (Hanau), Chemetall GmbH (Frankfurt),
BASF AG (Ludwigshafen) and Witco AG (Bergkamen)
for generous gift of chemicals.
References
1. (a) Knochel, P.; Jones, P. Eds. Organozinc Reagents: A
Practical Approach; Oxford University Press: Oxford, 1999.
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4-(3-Oxocyclohexyl)benzonitrile (3m). 1H NMR (200
MHz, CDCl3): d 1.65±1.89 (2H, m, CH2), 1.98±2.20 (2H,
m, CH2), 2.29±2.61 (4H, m,CH2), 2.95±3.15 (1H, m, CH),
7.30 (2H, d, Jˆ7.5 Hz, ArH), 7.60 (2H, d, Jˆ7.5 Hz, ArH).
13C NMR (75 MHz, CDCl3): 25.1 (CH2), 32.1 (CH2), 40.8
(CH2), 44.4 (CH), 48.0 (CH2), 110.4 (CN), 118.1 (ArC),
127.3, 132.4 (ArCH), 149.4 (ArC), 209.5 (CO). MS (EI):
199 (M1), 170(M1229), 103, 89. IR: (CHCl3): 2890±2990
(ArCH), 2220 (CN), 1715 (CO); (cm21). Anal. Calcd For
C13H13NO: C 78.36, H 6.58. Found: C 78.45, H 6.41
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37, 1385; 1980, 36, 2305. (b) Bourgain-Commercon, M.; Foulon,
J. P.; Normant, J. F. J. Organomet. Chem. 1982, 228, 321.
(c) Nakamura, E.; Kuwajima, I. J. Am. Chem. Soc. 1984, 106,
3368.
4-(3-Oxocyclopentyl)benzonitrile (3n). 1H NMR (200
MHz, CDCl3): d 1.81±2.05 (1H, m, CH2), 2.18±2.73 (5H,
m, CH2), 3.31±3.52 (1H, m, CH), 7.35 (2H, d, Jˆ7.2 Hz,
ArH), 7.61 (2H, d, Jˆ7.2 Hz, ArH). 13C NMR (75 MHz,
CDCl3): 30.7 (CH2), 38.5 (CH2), 42.1 (CH), 45.1 (CH2),
110.4 (CN), 118.6 (ArC), 127.5, 132.4 (ArCH), 148.4
(ArC), 216.8 (CO). MS (EI): 185 (M1), 156 (M1229),
129, 103. IR: (CHCl3): 2890±2990 (ArCH), 2215 (CN),
1722 (CO); (cm21). Anal. Calcd For C13H13NO: C 77.81,
H 5.99. Found: C 77.96, H 5.84.
7. (a) Corey, E. J.; Boaz, N. W. Tetrahedron Lett. 1985, 26, 6015
and 6019. (b) Alexakis, A.; Berlan, J.; Besace, Y. Tetrahedron Lett.
1986, 27, 1047.
8. (a) Horiguchi, Y.; Matsuzawa, S.; Nakamura, E.; Kuwajima, I.
Tetrahedron Lett. 1986, 27, 4025. (b) Nakamura, E.; Matsuzawa,
S.; Horiguchi, Y.; Kuwajima, I. Tetrahedron Lett. 1986, 27, 4029.
9. Matsuzawa, S.; Horiguchi, Y.; Nakamura, E.; Kuwajima, I.
Tetrahedron 1989, 45, 349.
10. Reetz, M. T.; Kindler, A. J. Chem. Soc., Chem. Commun.
1994, 2509.
1
4-(1,3-Diphenyl-3-oxopropyl)benzonitrile (3o). H NMR
(200 MHz, CDCl3): d 3.67 (2H, d, Jˆ7.5 Hz, CH2), 4.90
(1H, t, Jˆ7.2 Hz, CH), 7.05±7.55 (12H, m, ArH),7.63 (2H,
d, Jˆ7.8 Hz, ArH). 13C NMR (75 MHz, CDCl3): 44.4
11. For the use of CuX´2LiCl as soluble copper salts, see:
Knochel, P.; Yeh, M. C. P.; Berk, S. C.; Talbert, J. Org. Chem.
1988, 53, 2390.