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J. Jin, T. V. RajanBabu / Tetrahedron 56 (2000) 2145±2151
Heterodimerization of 4-chlorostyrene and propylene.
Following the procedure for hydrovinylation of styrene
using propylene, 4-chlorostyrene (0.24 ml, 2.00 mmol)
was converted to alkenes 7c and 8c at 08C as an inseparable
mixture (339 mg, 94%, 4:1 ratio; RT12.66 and 11.28 min,
condition B). 7c: 1H NMR (300 MHz, CDCl3) d 1.31
(d, J7.0 Hz, 3H), 1.65±1.69 (m, 3H), 3.32±3.44 (m),
3.65±3.80 (m, together with previous peak 1H), 5.39±
5.63 (m, 2H), 7.10±7.17 (m, 2H), 7.23±7.29 (m, 2H);
EI MS m/z (relative intensity) 182 (6), 180 (M1, 24);
HRMS calcd for C11H13Cl 180.0706, found 180.0710;
RT14.98 min; 8c: 1H NMR (300 MHz, CDCl3) d
1.35 (d, J7.1 Hz, 3H), 1.58 (s, 3H), 3.32±3.44 (m,
1H), 4.84±4.89 (m, 2H), 7.10±7.17 (m, 2H), 7.23±
7.29 (m, 2H).
Heterodimerization of 4-bis-toluenesulfonylaminostyrene
and propylene. Following the procedure for hydrovinyl-
ation of styrene using propylene, 4-bis-toluenesulfonylamino
styrene (427 mg, 1.00 mmol) was converted to alkenes 7g
and 8g as an inseparable mixture (431 mg, 92%, 2:1 ratio
1
determined by NMR). 7g: H NMR (300 MHz, CDCl3) d
1.33 (d, J7.0 Hz, 3H), 1.67±1.71 (m, 3H), 2.47 (s, 6H),
3.37±3.50 (m, 1H), 5.42±5.64 (m, 2H), 6.90±6.98 (m, 2H),
7.14±7.22 (m, 2H), 7.28±7.38 (m, 4H), 7.76±7.87 (m, 4H);
EI MS m/z (relative intensity) 469 (M1, 23); HRMS calcd
1
for C25H27NO4S2 469.1382, found 469.1406; 8g: H NMR
(300 MHz, CDCl3) d 1.37 (d, J7.1 Hz, 3H), 1.60 (s, 3H),
2.47 (s, 6H), 3.37±3.50 (m, 1H), 4.88 (s, 2H), 6.90±6.98 (m,
2H), 7.14±7.22 (m, 2H),7.28±7.38 (m, 4H), 7.76±7.87 (m,
4H); EI MS m/z (relative intensity) 469 (M1, 23); HRMS
calcd for C25H27NO4S2 469.1382, found 469.1406.
Heterodimerization of 4-bromostyrene and propylene.
Following the procedure for hydrovinylation of 4-chloro-
styrene using propylene, 4-bromostyrene (0.262 ml,
2.00 mmol) was converted to alkenes 7d and 8d as an
inseparable mixture (428 mg, 95%, 4:1 ratio; RT16.39
and 15.06 min, condition B). 7d: 1H NMR (300 MHz,
CDCl3) d 1.31 (d, J7.1 Hz, 3H), 1.64±1.71 (m, 3H),
3.30±3.44 (m), 3.71±3.81 (m, together with previous peak
1H), 5.38±5.62 (m, 2H), 7.05±7.14 (m, 2H), 7.38±7.45 (m,
2H); EI MS m/z (relative intensity) 226 (9), 224 (M1, 10);
HRMS calcd for C11H13Br 224.0201, found 224.0199; 8d:
1H NMR (300 MHz, CDCl3) d 1.35 (d, J7.0 Hz, 3H), 1.59
(s, 3H), 3.30±3.44 (m, 1H), 4.86±4.90 (m, 2H), 7.05±7.14
(m, 2H), 7.38±7.45 (m, 2H).
Heterodimerization of 4-¯uoro-4-phenylstyrene and
propylene. Following the procedure for hydrovinylation
of styrene using propylene, 3-¯uoro-4-phenyl styrene
(198, 1.00 mmol) was converted to alkenes 7h and 8h as
an inseparable mixture (228 mg, 95%, 4:1 ratio; RT31.78
and 30.67 min, condition B). Alkene 7h: 1H NMR
(250 MHz, CDCl3) d 1.38 (d, J7.0 Hz, 3H), 1.70±1.74
(m, 3H), 3.38±3.53 (m), 3.77±3.93 (m, with previous
speak 1H), 5.45±5.70 (m, 2H), 6.97±7.14 (m, 2H), 7.33±
7.60 (m, 6H); EI MS m/z (relative intensity) 240 (M1, 100);
HRMS calcd for C17H17F 240.1314, found 240.1313; alkene
8h: 1H NMR (250 MHz, CDCl3) d 1.42 (d, J7.1 Hz, 3H),
1.66 (s, 3H), 3.38±3.53 (m, 1H), 4.90±4.95 (m, 2H), 6.97±
7.14 (m, 2H), 7.33±7.60 (m, 2H); EI MS m/z (relative
intensity) 240 (M1, 100); HRMS calcd for C17H17F
240.1314, found 240.1313.
Heterodimerization of 4-acetoxystyrene and propylene.
Following the procedure for hydrovinylation of styrene
using propylene, 4-acetoxystyrene (0.31 ml, 2.00 mmol)
was converted to alkenes 7e and 8e as an inseparable
mixture (380 mg, 93%, 4:1 ratio; RT20.65 and
Heterodimerization of 2-methoxy-6-vinyl naphthalene
and propylene. Following the procedure for hydrovinyl-
ation of styrene using propylene, 2-methoxy-6-vinyl
naphthalene (184 mg, 1.00 mmol) was converted to alkenes
7i and 8i as an inseparable mixture (199 mg, 88%, 10:1
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19.35 min, condition B). 7e: H NMR (300 MHz, CDCl3)
d 1.32 (d, J7.0 Hz, 3H), 1.65±1.69 (m, 3H), 2.29 (s, 3H),
3.35±3.47 (m), 3.73±3.86 (m, together with previous peak
1H), 5.40±5.64 (m, 2H), 6.98±7.06 (m, 2H), 7.17±7.26 (m,
2H); EI MS m/z (relative intensity) 204 (M1, 6), 162 (37),
147 (100); HRMS calcd for C13H16O2 204.1150, found
204.1144; 8e: 1H NMR (300 MHz, CDCl3) d 1.36
(d, J7.1 Hz, 3H), 1.60 (s, 3H), 2.29 (s, 3H), 3.35±3.47
(m), 4.83±4.89 (m, 2H), 6.98±7.06 (m, 2H), 7.17±7.26
(m, 2H).
1
ratio; RT33.40 and 32.39 min, condition B). 7i: H NMR
(250 MHz, CDCl3) d 1.42 (d, J7.0 Hz, 3H), 1.66±1.75 (m,
3H), 3.48±3.65 (m, 1H), 3.92 (s, 3H), 5.44±5.77 (m, 2H),
7.08±7.76 (m, 6H); EI MS m/z (relative intensity) 226 (M1,
67), 211 (100); HRMS calcd for C16H18O 226.1358, found
226.1348; 8i: 1H NMR (250 MHz, CDCl3)(d 1.46 (d,
J7.1 Hz, 3H), 1.63 (s, 3H), 3.48±3.65 (m, 1H), 3.92 (s,
3H), 4.82±4.97 (m, 2H), 7.08±7.76 (m, 6H).
Heterodimerization of 4-vinylbenzophenone and propyl-
ene. Following the procedure for hydrovinylation of styrene
using propylene, 4-vinylbezophenone (208 mg, 1.00 mmol)
was converted to alkenes 7f and 8f as an inseparable mixture
(235 mg, 94%, 4:1 ratio; RT30.56 and 29.72 min, condi-
Heterodimerization of 2-methoxy-6-vinylnaphthalene
and propylene using [(allyl)NiBr]2, MOP (5,
RCH2Ph) and NaB[(3,5-CF3)2C6H3)]4. To a solution of
[(allyl)NiBr]2 (5.4 mg, 0.015 mmol) of CH2Cl2 (0.5 ml)
under nitrogen at room temperature was added a solution
of (R)±MOP±OBn (5, 16.4 mg, 0.03 mmol) in CH2Cl2
(1.5 ml). The resulting brown solution was added to a
solution of [Na]1[[3,5]-(CF3)2C6H3]4B]2 (37.2 mg,
0.042 mmol) in CH2Cl2 (2 ml). After stirring for 1.5 h at
room temperature, the mixture was ®ltered through a
small plug of Celite, and the precipitate was rinsed with
CH2Cl2 (1 ml). The ®ltrate was collected in a Schlenk
¯ask, and was taken out of the drybox. The catalyst solution
was cooled to 08C. Under one atmosphere of propylene, a
solution of 2-methoxy-6-vinylnaphthalene (0.184 g,
1
tion B, but initial temp. at 1508C for 10 min). 7f: H NMR
(250 MHz, CDCl3) d 1.38 (d, J7.0 Hz, 3H), 1.69±1.72 (m,
3H), 3.45±3.57 (m), 3.82±3.95 (m, together with previous
peak 1H), 5.44±5.70 (m, 2H), 7.28±7.85 (m, 9H); EI MS
m/z (relative intensity) 250 (M1, 40), 145 (35), 105 (100);
HRMS calcd for C18H18O 250.1358, found 250.1351; 8f: 1H
NMR (250 MHz, CDCl3) d 1.42 (d, J7.1 Hz, 3H), 1.63 (s,
3H), 3.45±3.57 (m, 1H), 4.89±4.97 (m, 2H), 7.28±7.85 (m,
9H); EI MS m/z (relative intensity) 250 (M1, 40), 145 (35),
105 (100); HRMS calcd for C18H18O 250.1358, found
250.1351.