AllylSmBr as a Grignard and SET Reagent
FULL PAPER
CH2CH), 5.07–5.14 (m, 4H; 2ꢁCH=CH2), 5.80–5.91 (m, 2H; 2ꢁCH=
CH2), 6.34 (s, 1H; CH=C), 7.14–7.27 ppm (m, 4H; Ar); 13C NMR
(100 MHz, CDCl3): d=35.78, 42.00 (2ꢁCH2CH), 116.79, 117.29, 126.61,
128.71, 130.21, 132.48, 136.00, 136.50, 136.82, 139.95 ppm (4ꢁCAr, 6ꢁ
(100 MHz, CDCl3): d=44.13 (CH2CH), 116.91, 117.11, 126.98, 127.12,
127.80, 128.33, 128.55, 128.68, 128.80, 136.43, 141.22, 141.24, 143.26,
145.23 ppm (8ꢁCAr, 6ꢁCalkene); HRMS (EI+): m/z calcd for C19H18
246.1409 [M]+; found: 246.1418.
:
C
alkene); HRMS (EI+): m/z calcd for C14H1535Cl: 218.0862 [M]+; found:
(4-Allylhepta-1,3,6-trien-2-yl)benzene (11a): Compound 11a was ob-
218.0859; C14H1537Cl: 220.0833 [M]+; found: 220.0856.
tained according to the general procedure. Colourless oil; yield: 75%;
3
Rf =0.87 (PE); 1H NMR (400 MHz, CDCl3): d=2.89 (d, JH,H =8.0 Hz,
1-(2-Allylpenta-1,4-dienyl)-4-methylbenzene (7c): Compound 7c was ob-
tained according to the general procedure. Colourless oil; yield: 61%;
Rf =0.95 (PE); 1H NMR (400 MHz, CDCl3): d=2.33 (s, 3H; CH3), 2.89–
2.99 (m, 4H; 2ꢁCH2CH), 5.08–5.12 (m, 4H; 2ꢁCH=CH2), 5.82–5.92 (m,
2H; 2ꢁCH=CH2), 6.37 (s, 1H; CH=C), 7.10–7.15 ppm (m, 4H; Ar);
13C NMR (100 MHz, CDCl3): d=21.62 (CH3), 35.84, 42.03 (2ꢁ CH2CH),
116.55, 116.96, 127.62, 128.83, 129.29, 135.51, 136.38, 136.45, 136.92,
3
2H; CH2CH), 2.92 (d, JH,H =8.0 Hz, 2H; CH2CH), 5.00–5.14 (m, 5H;
2ꢁCH2=CH, CH2a=C), 5.52 (s, 1H; CH2b=C), 5.71–5.92 (m, 2H; 2ꢁCH=
3
CH2), 6.05 (s, 1H; CH=C), 7.24–7.31 (m, 3H; Ar), 7.40 ppm (d, JH,H
=8.0 Hz, 2H; Ar); 13C NMR (75 MHz, CDCl3): d=36.22, 41.32 (2ꢁ
CH2CH), 114.43, 116.49, 117.02, 126.93, 127.37, 127.99, 128.67, 136.75,
136.83, 140.73, 141.31, 145.12 ppm (4ꢁCAr, 8ꢁCalkene); HRMS (EI+): m/z
calcd for C16H18: 210.1409 [M]+; found: 210.1404.
138.41 ppm (4ꢁCAr, 6ꢁCalkene); HRMS (EI+): m/z calcd for C15H18
198.1409 [M]+; found: 198.1418.
:
1-(4-Allylhepta-1,3,6-trien-2-yl)-4-fluorobenzene (11b): Compound 11b
(3-Allylhexa-2,5-dienyl)benzene (7d): Compound 7d was obtained ac-
cording to the general procedure. Colourless oil; yield: 69%; Rf =0.75
(PE); 1H NMR (400 MHz, CDCl3): d=2.77–2.89 (m, 4H; 2ꢁCH2CH=
was obtained according to the general procedure. Colourless oil; yield:
3
92%; Rf =0.92 (PE); 1H NMR (400 MHz, CDCl3): d=2.90 (t, JH,H
=8.0 Hz, 4H; 2ꢁCH2CH), 5.00–5.12 (m, 5H; 2ꢁCH2=CH, CH2a=C),
5.46 (s, 1H; CH2b=C), 5.71–5.92 (m, 2H; 2ꢁCH=CH2), 6.01 (s, 1H; CH=
C), 6.97–7.02 (m, 2H; Ar), 7.34–7.38 ppm (m, 2H; Ar); 13C NMR
3
CH2), 3.38 (d, JH,H =7.2 Hz, 2H; CH2CH=C); 5.01–5.09 (m, 4H; 2ꢁ
3
CH=CH2), 5.44 (t, JH,H =7.2 Hz, 1H; CH=C), 5.72–5.84 (m, 2H; 2ꢁ
CH=CH2), 7.16–7.28 ppm (m, 5H; Ar); 13C NMR (100 MHz, CDCl3): d=
34.57, 35.09 (2ꢁCH2CH=CH2), 41.85 (ArCH), 116.02, 116.56, 126.04,
126.28, 128.82, 128.83, 136.20, 136.63, 137.15, 141.73 ppm (4ꢁCAr, 6ꢁ
Calkene); HRMS (EI+): m/z calcd for C15H18: 198.1409 [M]+; found:
198.1414.
(75 MHz, CDCl3): d=36.24, 41.33 (2ꢁCH2CH), 114.27 (4JC,F
=
9.0 Hz),115.36, 115.64, 116.60, 117.15, 127.18, 128.57 (3JC,F =8.3 Hz),
136.69 (2JC,F =3.7 Hz), 141.08, 144.13, 162.91 ppm (1JC,F =245.3 Hz, 4ꢁ
CAr, 7ꢁCalkene); HRMS (EI+): m/z calcd for C16H17F: 228.1314 [M]+;
found: 228.1315.
Hepta-1,6-dien-4-ylidenecyclohexane (7e): Compound 7e was obtained
according to the general procedure. Colourless oil; yield: 51%; Rf =0.83
(PE); 1H NMR (400 MHz, CDCl3): d=1.51–1.57 (m, 6H; CH2CH2CH2),
1-(4-Allylhepta-1,3,6-trien-2-yl)-4-chlorobenzene (11c): Compound 11c
was obtained according to the general procedure. Colourless oil; yield:
3
87%; Rf =0.90 (PE); 1H NMR (400 MHz, CDCl3): d=2.89 (d, JH,H
3
3
2.15 (t, JH,H =6.0 Hz, 4H; CH2CCH2), 2.77 (d, JH,H =5.6 Hz, 4H; 2ꢁ
CH2CH), 4.94–5.01 (m, 4H; 2ꢁCH=CH2), 5.69–5.79 ppm (m, 2H; 2ꢁ
CH=CH2); 13C NMR (100 MHz, CDCl3): d=27.38, 28.83, 31.08 (2ꢁCH2),
36.62 (CH2CH), 114.91, 124.18, 136.73, 137.48 ppm (4ꢁCalkene); HRMS
(EI+): m/z calcd for C13H20: 176.1565 [M]+; found: 176.1557.
=8.0 Hz, 4H; 2ꢁCH2CH), 5.00–5.15 (m, 5H; 2ꢁCH2=CH, CH2a=C),
5.50 (s, 1H; CH2b=C), 5.70–5.91 (m, 2H; 2ꢁCH=CH2), 6.00 (s, 1H; CH=
C), 7.24–7.33 ppm (m, 4H; Ar); 13C NMR (75 MHz, CDCl3): d=36.26,
41.33 (2ꢁCH2CH), 114.89,116.64, 117.18, 126.88, 128.26, 128.83, 133.85,
136.62, 139.79, 141.34, 144.09 ppm (4ꢁCAr, 8ꢁCalkene); HRMS (EI+): m/z
calcd for C16H1735Cl (M+): 244.1019; found: 244.1020; C16H1737Cl:
246.0989 [M]+; found: 246.0979.
4-Allylundeca-1,4-diene (7 f): Compound 7 f was obtained according to
the general procedure. Colourless oil; yield: 70%; Rf =0.85 (PE);
3
1H NMR (400 MHz, CDCl3): d=0.88 (t, JH,H =7.2 Hz, 3H; CH3), 1.27–
1-(4-Allylhepta-1,3,6-trien-2-yl)-4-bromobenzene (11d): Compound 11d
1.33 (m, 8H; CH2CH2CH2CH2OH), 1.98–2.03 (m, 2H; CH2CH=C), 2.71–
2.78 (m, 4H; 2ꢁCH2CH=CH2), 4.97–5.04 (m, 4H; 2ꢁCH=CH2), 5.24 (t,
3JH,H =7.2 Hz, 1H; CH=C), 5.68–5.82 ppm (m, 2H; 2ꢁCH=CH2);
13C NMR (100 MHz, CDCl3): d=14.59 (CH3), 23.16, 28.37, 29.57, 30.38,
32.30 (CH2 CH2CH2CH2CH2), 35.07, 41.83 (2ꢁCH2CH=CH2), 115.61,
116.18, 127.86, 135.38, 136.66, 137.59 ppm (6ꢁCalkene); HRMS (EI+): m/z
calcd for C14H24: 192.1878 [M]+; found: 192.1867.
was obtained according to the general procedure. Colourless oil; yield:
3
85%; Rf =0.90 (PE); 1H NMR (400 MHz, CDCl3): d=2.89 (d, JH,H
=8.0 Hz, 4H; 2ꢁCH2CH), 4.99–5.16 (m, 5H; 2ꢁCH2=CH, CH2a=C),
5.50 (s, 1H; CH2b=C), 5.70–5.91 (m, 2H; 2ꢁCH=CH2), 5.99 (s, 1H; CH=
3
3
C), 7.26 (d, JH,H =8.0 Hz, 2H; Ar), 7.43 (d, JH,H =8.0 Hz, 2H; Ar);
13C NMR (75 MHz, CDCl3): d=36.25, 41.32 (2ꢁCH2CH), 114.96, 116.65,
117.20, 122.03, 126.77, 128.59, 131.77, 136.59, 140.23, 141.38, 144.10 ppm
(4ꢁCAr, 8ꢁCalkene); HRMS (EI+): m/z calcd for C16H1779Br: 288.0514
[M]+; found: 288.0514; m/z calcd for C16H1781Br: 290.0493 [M]+; found:
290.0515.
4,7-Diallyldeca-1,4,6,9-tetraene (7g): Compound 7g was obtained accord-
ing to the general procedure. Colourless oil; yield: 57%; Rf =0.80 (PE);
1H NMR (400 MHz, CDCl3): d=2.81–2.92 (m, 8H; 4ꢁCH2CH=CH2),
5.00–5.06 (m, 8H; 4ꢁCH=CH2), 5.70–5.84 (m, 4H; 4ꢁCH=CH2),
6.11 ppm (s, 2H; CHCH); 13C NMR (100 MHz, CDCl3): d=35.47, 42.35
(2ꢁCH2CH), 116.11, 116.82, 122.64, 136.22, 136.89, 137.80 ppm (6ꢁ
Calkene); HRMS (EI+): m/z calcd for C16H22: 173.1331 [MÀC3H5]+; found:
173.1300.
1-(4-Allylhepta-1,3,6-trien-2-yl)-2-bromobenzene (11e): Compound 11e
was obtained according to the general procedure. Colourless oil; yield:
3
86%; Rf =0.88 (PE); 1H NMR (400 MHz, CDCl3): d=2.75 (d, JH,H
3
=8.0 Hz, 2H; CH2CH), 2.82 (d, JH,H =8.0 Hz, 2H; CH2CH), 4.91–5.13
(m, 5H; 2ꢁCH2=CH, CH2a=C), 5.36 (s, 1H; CH2b=C), 5.61–5.86 (m, 2H;
2ꢁCH=CH2), 6.00 (s, 1H; CH=C), 7.10–7.56 ppm (m, 4H; Ar); 13C NMR
(75 MHz, CDCl3): d=35.94, 42.00 (2ꢁCH2CH), 116.44, 117.04, 119.26,
122.84, 127.35, 127.68, 129.05, 130.98, 133.24, 136.34, 136.65, 139.68,
4-Allylhepta-3,6-dien-1-ol (7h): Compound 7h was obtained according to
the general procedure. Yellow oil; yield: 42%; Rf =0.33 ( PE/EtOAc
5:1); 1H NMR (400 MHz, CDCl3): d=1.84 (brs, 1H; OH); 2.30–2.35 (m,
143.96, 146.51 ppm (6ꢁCAr,
8ꢁCalkene); HRMS (EI+): m/z calcd for
3
2H; CH2CH=C), 2.76–2.82 (m, 4H; 2ꢁCH2CH=CH2), 3.62–3.65 (t, JH,H
C16H1779Br: 288.0514 [M]+; found: 288.0514; C16H1781Br: 290.0493 [M]+;
3
=6.4 Hz, 2H; CH2OH), 5.00–5.66 (m, 4H; 2ꢁCH=CH2), 5.26 (t, JH,H
=7.2 Hz, 1H; CH=C), 5.73–5.81 ppm (m, 2H; 2ꢁCH=CH2); 13C NMR
(100 MHz, CDCl3): d=31.86 (CH2CH2OH), 35.13 (CaH2CH=CH2), 41.86
(CbH2CH=CH2), 62.85 (CH2OH), 115.95, 116.65, 122.87, 136.28, 137.03,
139.12 ppm (6ꢁCalkene); HRMS (EI+): m/z calcd for C10H16: 152.1501
[M]+; found: 152.1512.
found: 290.0515.
1-(4-Allylhepta-1,3,6-trien-2-yl)-4-methoxybenzene (11 f): Compound 11 f
was obtained according to the general procedure. Colourless oil; yield:
73%; Rf =0.78 (PE); 1H NMR (400 MHz, CDCl3): d=2.89 (d, JH,H
3
3
=8.0 Hz, 2H; CH2CH), 2.93 (d, JH,H =8.0 Hz, 2H; CH2CH), 3.81 (s, 3H;
OCH3), 5.00–5.13 (m, 5H; 2ꢁCH2=CH, CH2a=C), 5.45 (d, JH,H =4.0 Hz,
3
ACHTUNGTRENNUNG(Z,E)-Hepta-1,3,6-triene-2,4-diyldibenzene (9): Compound 9 was ob-
1H; CH2b=C), 5.72–5.93 (m, 2H; 2ꢁCH=CH2), 6.03 (s, 1H; CH=C), 6.86
tained according to the general procedure. Colourless oil; yield: 73%;
3
3
3
Rf =0.86 (PE); 1H NMR (400 MHz, CDCl3): d=3.15 (d, JH,H =6.4 Hz,
(d, JH,H =12.0 Hz, 2H; Ar), 7.34 ppm (d, JH,H =8.0 Hz, 2H; Ar);
13C NMR (75 MHz, CDCl3): d=36.25, 41.30 (2ꢁCH2CH), 55.77 (OCH3),
112.72, 114.04, 116.47, 117.00, 127.59, 128.07, 133.84, 136.84, 136.98,
140.55, 144.43, 159.68 ppm (4ꢁCAr, 8ꢁCalkene); HRMS (EI+): m/z calcd
for C17H20O: 240.1514 [M]+; found: 240.1514.
3
2H; CH2CH; Z isomer). 3.34 (d, JH,H =4.8 Hz, 2H; CH2CH; E isomer),
4.80 (s, 1H; CH2a=C), 4.96–5.04 (m, 2H; CH2=CH), 5.20 (s, 1H; CH2b=
C), 5.76–5.86 (m, 1H; CH=CH2), 6.15 (s, 1H; CH=C; Z isomer), 6.50 (s,
1H; CH=C;
E
isomer), 7.03–7.29 ppm (m, 10H; Ar); 13C NMR
Chem. Eur. J. 2010, 16, 1697 – 1705
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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