Cross-Coupling Reactions
FULL PAPER
(q, 3J
ACHTREUNG
G
G
(C), 127.3 (CH), 126.9 (CH), 124.8 (CH), 124.4 (CH), 108.8 (C), 85.5 (C),
37.5 (CH), 34.8 (CH2), 31.7 (CH2), 0.16 ppm (3CH3); MS (70 eV, EI):
m/z (%): 214 [M+] (32), 199 [M+ÀCH3] (34), 117 (69), 84 (92), 73 (100);
HRMS (EI): m/z: calcd for C14H18Si: 214.1172 [M+]; found: 214.1168;
165.7 (C), 134.4 (C), 128.6 (2CH), 127.8 (CH), 126.2 (2CH), 105.4
(C), 89.8 (CH), 60.9 (CH2), 16.2 (CH3), 14.3 ppm (CH3); IR (CHCl3): n˜ =
1948 (C=C=C), 1718 cmÀ1 (C=O); MS (70 eV, EI): m/z (%): 202 [M+]
(20), 174 (38), 158 (25), 129 (100); HRMS (EI): m/z: calcd for C13H14O2:
202.0988 [M+]; found: 202.0987; HPLC (Chiralcel OD-H): eluent:
iPrOH/hexane 0.5:99.5, flow: 0.5 mLminÀ1
HPLC (Chiralcel OD-H): eluent: hexane, flow: 0.5 mLminÀ1
.
1-(Phenylethynyl)-1,2-dihydrocyclobutabenzene (15): According to the
general procedure, the reaction of (Æ)-1-bromobenzocyclobutane (10,
126 mg, 0.690 mmol) with tri(phenylethynyl)indium (0.28 mmol) afford-
ed, after purification by column chromatography (hexanes), compound
15 as a colorless oil (113 mg, 81%, 6% ee). 1H NMR (300 MHz, CDCl3,
(3-Phenyl-1-butynyl)trimethylsilane (8):[18] According to the general pro-
cedure, the reaction of (Æ)-a-methylbenzylbromide (1, 132 mg,
0.722 mmol) with tris(trimethylsilylethynyl)indium (0.29 mmol) afforded,
after purification by column chromatography (hexanes), compound 8 as a
colorless oil (82 mg, 57%). 1H NMR (300 MHz, CD2Cl2, 258C): d=7.42–
258C): d=7.50–7.15 (m, 9H), 4.49 (dd, J
ACHTREUNG
(dd, J(H,H)=13.7, 5.5 Hz, 1H), 3.42 ppm (dd, JACHTREUNG
G
1H); 13C NMR (75 MHz, CDCl3, 258C): d=145.2 (C), 143.6 (C), 131.6
(2CH), 128.2 (2CH), 128.0 (CH), 127.7 (CH), 127.4 (CH), 123.6 (C),
123.2 (CH), 122.1 (CH), 89.7 (C), 82.3 (C), 38.9 (CH2), 32.6 ppm (CH);
MS (70 eV, EI): m/z (%): 204 [M+] (88), 202 (100), 101 (20); HRMS
(EI): m/z: calcd for C16H12: 204.0934 [M+]; found: 204.0934; HPLC
7.25 (m, 5H), 3.80 (q, 3J(H,H)=7.1 Hz, 1H), 1.49 (d, 3J
ACTHERNGU ACHTRE(UGN H,H)=7.1 Hz,
3H), 0.20 ppm (s, 9H); 13C NMR (75 MHz, CD2Cl2, 258C): d=143.6 (C),
128.9 (2CH), 127.3 (2CH), 127.0 (CH), 109.9 (C), 86.4 (C), 32.2
(CH), 24.8 (CH3), 0.2 ppm (3CH3); MS (70 eV, EI): m/z (%): 202 [M+]
(11), 187 [M+ÀCH3] (43), 159 (18), 105 (100); HRMS (EI): m/z: calcd
for C13H18Si: 202.1172 [M+]; found: 202.1168.
(Chiralcel OD-H): eluent: iPrOH/hexane 0.5:99.5, flow: 0.5 mLminÀ1
.
2-[(1,2-Dihydrocyclobutabenzen-1-yl)ethynyl]-6-methoxynaphthalene
(16): According to the general procedure, the reaction of (Æ)-1-bromo-
benzocyclobutane (10, 128 mg, 0.700 mmol) with tri[(6-methoxy-2-naph-
thalenyl)ethynyl]indium (0.28 mmol) afforded, after purification by
1-(Phenylethynyl)-2,3-dihydro-1H-indene (11):[19] According to the gener-
al procedure, the reaction of (Æ)-1-bromoindane (9, 140 mg, 95%,
0.675 mmol) with tri(phenylethynyl)indium (0.27 mmol) afforded, after
purification by column chromatography (hexanes), compound 11 as a
white solid (96 mg, 65%, 82% ee). M.p. 79–818C; 1H NMR (300 MHz,
column chromatography (hexanes), compound 16 as
(113 mg, 55%, 6% ee). M.p. 83–848C; 1H NMR (300 MHz, CDCl3,
258C): d=7.90–7.11 (m, 10H), 4.52 (dd, J(H,H)=5.5, 2.8 Hz, 1H), 3.93
(s, 3H), 3.74 (dd, J(H,H)=13.9, 5.6 Hz, 1H), 3.44 ppm (dd, J(H,H)=
a white solid
CDCl3, 258C): d=7.54–7.25 (m, 9H), 4.25 (t, 3J
ACHTRE(UNG H,H)=8.5 Hz, 1H),
AHCTREUNG
3.12–2.90 (m, 2H), 2.63 (m, 1H), 2.25 ppm (m, 1H); 13C NMR (75 MHz,
CDCl3, 258C): d=143.6 (C), 142.9 (C), 131.7 (CH), 128.2 (CH), 127.7
(CH), 127.0 (CH), 126.6 (CH), 124.5 (CH), 124.3 (CH), 123.7 (C), 91.5
(C), 81.6 (C), 36.8 (CH), 34.4 (CH2), 31.5 ppm (CH2); MS (70 eV, EI):
m/z (%): 218 [M+] (100), 203 [M+ÀCH3] (51), 189 (14), 115 (34); HRMS
(EI): m/z: calcd for C17H14: 218.1090 [M+]; found: 218.1086; HPLC
A
ACHTREUNG
13.9, 2.9 Hz, 1H); 13C NMR (75 MHz, CDCl3, 258C): d=158.1 (C), 145.3
(C), 143.6 (C), 133.8 (C), 131.1 (CH), 129.2 (CH), 129.1 (CH), 128.4 (C),
128.0 (CH), 127.4 (CH), 126.6 (CH), 123.2 (CH), 122.1 (CH), 119.2
(CH), 118.4 (C), 105.7 (CH), 89.3 (C), 82.7 (C), 55.2 (CH3), 39.0 (CH2),
32.8 ppm (CH); MS (70 eV, EI): m/z (%): 284 [M+] (72), 269 [M+ÀCH3]
(22), 241 (100); HRMS (EI): m/z: calcd for C21H16O: 284.1196 [M+];
found: 284.1200; HPLC (Chiralcel OD-H): eluent: iPrOH/hexane
(Chiralcel OD-H): eluent: hexane, flow: 0.5 mLminÀ1
2-[(2,3-Dihydro-1H-inden-1-yl)ethynyl]-6-methoxynaphthalene (12): A c-
cording to the general procedure, the reaction of (Æ)-1-bromoindane (9,
138 mg, 97%, 0.678 mmol) with tri[(6-methoxy-2-naphthalenyl)ethynyl]-
indium (0.27 mmol) afforded, after purification by column chromatogra-
phy (1% Et2O/hexanes), compound 12 as a white solid (121 mg, 60%,
81% ee). M.p. 100–1018C; 1H NMR (300 MHz, CDCl3, 258C): d=7.90–
0.5:99.5; flow: 0.5 mLminÀ1
.
3-[(1,2-Dihydrocyclobutabenzen-1-yl)ethynyl]thiophene (17): According
to the general procedure, the reaction of (Æ)-1-bromobenzocyclobutane
(10, 128 mg, 0.700 mmol) with tri[(3-thienyl)ethynyl]indium (0.28 mmol)
afforded, after purification by column chromatography (hexanes), com-
pound 17 as a colorless oil (96 mg, 65%, 7% ee). 1H NMR (300 MHz,
7.11 (m, 10H), 4.27 (t, 3J
ACHTRE(UNG H,H)=8.5 Hz, 1H), 3.93 (s, 3H), 3.12–2.90 (m,
2H), 2.64 (m, 1H), 2.26 ppm (m, 1H); 13C NMR (75 MHz, CDCl3, 258C):
d=158.1 (C), 143.7 (C), 143.0 (C), 133.8 (C), 131.0 (CH), 129.3 (CH),
129.2 (CH), 128.5 (C), 127.1 (CH), 126.6 (2CH), 124.5 (CH), 124.3
(CH), 119.2 (CH), 118.7 (C), 105.8 (CH), 91.1 (C), 82.0 (C), 55.3 (CH3),
36.9 (CH), 34.5 (CH2), 31.5 ppm (CH2); MS (70 eV, EI): m/z (%): 298
[M+] (100), 283 [M+ÀCH3] (30), 252 (33), 239 (23); HRMS (EI): m/z:
calcd for C22H18O: 298.1352 [M+]; found: 298.1350; HPLC (Chiralcel
CDCl3, 258C): d=7.42–7.11 (m, 7H), 4.45 (dd, J
ACHTREUNG
3.70 (dd, J(H,H)=14.0, 5.5 Hz, 1H), 3.36 ppm (dd, JACHTREUNG
A
1H); 13C NMR (75 MHz, CDCl3, 258C): d=145.1 (C), 143.5 (C), 129.9
(CH), 128.0 (2CH), 127.4 (CH), 125.0 (CH), 123.2 (CH), 122.5 (C),
122.1 (CH), 89.2 (C), 77.4 (C), 38.2 (CH2), 32.6 ppm (CH); MS (70 eV,
EI): m/z (%): 210 [M+] (100), 165 (73); HRMS (EI): m/z: calcd for
C14H10S: 210.0498 [M+]; found: 210.0493; HPLC (Chiralcel OD-H):
eluent: hexane, flow: 0.5 mLminÀ1
.
OJ): eluent: iPrOH/hexane 30:70, flow: 1.0 mLminÀ1
[(1,2-Dihydrocyclobutabenzen-1-yl)ethynyl]trimethylsilane (18): Accord-
ing to the general procedure, the reaction of (Æ)-1-bromobenzocyclobu-
tane (10, 126 mg, 0.690 mmol) with tris(trimethylsilylethynyl)indium
(0.28 mmol) afforded, after purification by column chromatography (hex-
anes), compound 18 as a colorless oil (113 mg, 82%, 7% ee). 1H NMR
3-[(2,3-Dihydro-1H-inden-1-yl)ethynyl]thiophene (13): According to the
general procedure, the reaction of (Æ)-1-bromoindane (9, 140 mg, 97%,
0.689 mmol) with tri[(3-thienyl)ethynyl]indium (0.28 mmol) afforded,
after purification by column chromatography (hexanes), compound 13 as
a white solid (87 mg, 56%, 84% ee). M.p. 64–658C; 1H NMR (300 MHz,
(300 MHz, CDCl3, 258C): d=7.29–7.03 (m, 4H), 4.28 (dd, J
ACHTREUNG
CDCl3, 258C): d=7.52–7.13 (m, 7H), 4.22 (t, 3J
ACHTRE(UNG H,H)=8.5 Hz, 1H),
3.0 Hz, 1H), 3.62 (dd, J(H,H)=13.9, 5.6 Hz, 1H), 3.30 (dd, JACHTREUNG
G
3.10–2.89 (m, 2H), 2.61 (m, 1H), 2.24 ppm (m, 1H); 13C NMR (75 MHz,
CDCl3, 258C): d=143.5 (C), 142.9 (C), 130.0 (CH), 127.9 (CH), 127.1
(CH), 126.6 (CH), 125.0 (CH), 124.5 (CH), 124.3 (CH), 122.7 (C), 91.0
(C), 76.6 (C), 36.8 (CH), 34.3 (CH2), 31.5 ppm (CH2); MS (70 eV, EI):
m/z (%): 224 [M+] (100), 208 (21), 191 (29), 178 (21); HRMS (EI): m/z:
calcd for C15H12S: 224.0654 [M+]; found: 224.0654; HPLC (Chiralcel
14.1, 2.9 Hz, 1H), 0.20 ppm (s, 9H); 13C NMR (75 MHz, CDCl3, 258C):
d=145.0 (C), 143.6 (C), 127.9 (CH), 127.4 (CH), 123.1 (CH), 122.0 (CH),
106.4 (CH), 86.3 (C), 38.8 (CH2), 32.9 (CH), 0.1 ppm (3CH3); MS
(70 eV, EI): m/z (%): 200 [M+] (4), 185 [M+ÀCH3] (100), 172 (17), 141
(23); HRMS (EI): m/z: calcd for C13H16Si: 200.1016 [M+]; found:
200.1011; HPLC (Chiralcel OD-H): eluent: hexane, flow: 0.4 mLminÀ1
.
OD-H): eluent: hexane, flow: 0.5 mLminÀ1
.
[(2,3-Dihydro-1H-inden-1-yl)ethynyl]trimethylsilane (14): According to
the general procedure, the reaction of (Æ)-1-bromoindane (9, 142 mg,
97%, 0.700 mmol) with tris(trimethylsilylethynyl)indium (0.28 mmol) af-
forded, after purification by column chromatography (hexanes), com-
pound 14 as a colorless oil (60 mg, 40%, 80% ee). 1H NMR (300 MHz,
Acknowledgements
CDCl3, 258C): d=7.36 (m, 1H), 7.24–7.15 (m, 3H), 4.00 (dd, J
A
This research was supported by the Spanish Ministerio de Educación y
Ciencia (CTQ2006–06166), the Xunta de Galicia (PGIDIT04P-
XIC10308PN), and the FEDER.
9.0, 8.5 Hz, 1H), 2.95–2.85 (m, 2H), 2.49 (m, 1H), 2.05 (m, 1H),
0.17 ppm (s, 9H); 13C NMR (75 MHz, CDCl3, 258C): d=143.8 (C), 143.5
Chem. Eur. J. 2008, 14, 741 – 746
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
745