Organometallics
Article
were performed on the mixture of products, but only data of branched
product 3qa are given. 1H NMR (500 MHz, CDCl3) δ7.28−7.26 (m,
1H), 7.25 (t, J = 1.9 Hz, 2H), 7.24 (d, J = 2.6 Hz, 1H), 5.98 (dd, J =
17.5, 10.8 Hz, 1H), 5.07 (ddd, J = 18.7, 14.1, 1.2 Hz, 2H), 1.86−1.68
(m, 2H), 1.33 (s, 3H), 0.76 (t, J = 7.4 Hz, 3H). 13C NMR (126 MHz,
CDCl3) δ 146.4, 145.9, 128.2, 128.0, 126.8, 112.2, 44.3, 33.4, 24.4,
8.8. EI-MS: m/z 194.1 [M]+. HRMS (EI) m/z calcd for C12H15Cl
[M]+: 194.0862. Found: 194.0858. The absolute configuration was
assigned by analogy based on 3wa through a similar stereochemical
model. Enantiomeric excess was determined by chiral HPLC:
Chiralcel OJ-H column, n-hexane/i-PrOH = 100/0, flow rate 0.5
mL/min, 210 nm, retention times (min): 9.17 (minor) and 9.73
(major).
PrOH = 100/0, flow rate 0.5 mL/min, 210 nm, retention times
(min): 8.75 (minor) and 9.40 (major).
(R)-1′-Chloro-3′-(3-methylpent-1-en-3-yl)benzene (3va). Color-
less oil; 73% yield; 3va/4va = 81/19; 88% ee. NMR experiments were
performed on the mixture of products, but only data of branched
product 3va are given. 1H NMR (500 MHz, CDCl3) δ 7.29 (t, J = 1.7
Hz, 1H), 7.24−7.21 (m, 1H), 7.21−7.18 (m, 1H), 7.18−7.15 (m,
1H), 5.98 (dd, J = 17.5, 10.8 Hz, 1H), 5.16−5.02 (m, 2H), 1.86−1.69
(m, 2H), 1.34 (s, 3H), 0.77 (t, J = 7.4 Hz, 3H,). 13C NMR (126 MHz,
CDCl3) δ 149.7, 146.1, 129.2, 127.1, 125.9, 124.9, 112.4, 44.6, 33.3,
24.3, 8.8. EI-MS: m/z 194.0 [M]+. HRMS (EI) m/z calcd for
C12H15Cl [M]+: 194.0862. Found: 194.0867. The absolute config-
uration was assigned by analogy based on 3wa through a similar
stereochemical model. Enantiomeric excess was determined by chiral
HPLC: Chiralcel OJ-H column: n-hexane/i-PrOH = 100/0, flow rate
0.5 mL/min, 210 nm, retention times (min): 7.53 (minor) and 8.19
(major).
(R)-1′-(3-Methylpent-1-en-3-yl)-4′-(trifluoromethyl) benzene
(3ra). Colorless oil; 68% yield; 3ra/4ra = 84/16; 82% ee. NMR
experiments were performed on the mixture of products, but only data
1
of branched product 3ra are given. H NMR (500 MHz, CDCl3) δ
(R)-1′-(3-Methylpent-1-en-3-yl)-3′-(trifluoromethyl)benzene
7.55 (d, J = 8.3 Hz, 2H), 7.43 (d, J = 8.3 Hz, 2H), 6.00 (dd, J = 17.5,
10.8 Hz, 1H), 5.26−4.93 (m, 2H), 1.94−1.67 (m, 2H), 1.37 (s, 3H),
0.77 (t, J = 7.4 Hz, 3H).13C NMR (126 MHz, CDCl3) δ 151.6, 145.9,
127.1, 125.8, 124.9 (q, J = 3.8 Hz), 112.6, 44.7, 33.4, 24.3, 8.8. 19F
NMR (282 MHz, CDCl3) δ −62.7. EI-MS: m/z 228.2 [M]+. HRMS
(EI) m/z calcd for C13H15F3 [M]+: 228.1126. Found: 228.1134. The
absolute configuration was assigned by analogy based on 3wa through
a similar stereochemical model. Enantiomeric excess was determined
by chiral HPLC: Phenomenex Lux 5u Cellulose-3 (0.46 × 25 cm),
CH3CN/H2O = 75/25, 0.7 mL/min, 214 nm, retention times (min):
6.24 (minor) and 6.49 (major).
(R)-1′-Methyl-4′-(3-methylpent-1-en-3-yl)benzene (3sa). Color-
less oil; 56% yield; 3sa/4sa = 78/22; 54% ee. NMR experiments were
performed on the mixture of products, but only data of branched
product 3sa are given. 1H NMR (500 MHz, CDCl3) δ 7.21 (d, J = 8.1
Hz, 2H), 7.12 (d, J = 7.9 Hz, 2H), 6.01 (dd, J = 17.5, 10.8 Hz, 1H),
5.06 (dd, J = 28.8, 14.1 Hz, 2H), 2.32 (s, 3H), 1.88−1.68 (m, 2H),
1.33 (s, 3H), 0.77 (t, J = 7.4 Hz, 3H). 13C NMR (126 MHz, CDCl3)
δ 147.1, 144.5, 128.8, 128.7, 126.6, 111.5, 44.2, 33.4, 24.4, 20.8, 8.9.
EI-MS: m/z 174.0 [M]+. HRMS (EI) m/z calcd for C13H18 [M]+:
174.1409. Found: 174.1416. The absolute configuration was assigned
by analogy based on 3wa through a similar stereochemical model.
Enantiomeric excess was determined by chiral HPLC: Chiralcel OJ-H
column: n-hexane/i-PrOH = 100/0, flow rate 0.7 mL/min, 210 nm,
retention times (min): 10.12 (minor) and 13.16 (major).
(3wa). Colorless oil; 70% yield; 3wa/4wa = 86/14; 84% ee. [α]D25
−
20
10.9° (c = 0.5, CHCl3); lit. [α]D − 14.2° (c = 1.07, CHCl3) (30/1
b/l, 88% ee, R).25 NMR experiments were performed on the mixture
1
of products, but only data of branched product 3wa are given. H
NMR (500 MHz, CDCl3) δ 7.56 (s, 1H), 7.51 (d, J = 7.6 Hz, 1H),
7.48−7.43 (m, 1H), 7.42 (d, J = 7.7 Hz, 1H), 6.00 (dd, J = 17.5, 10.8
Hz, 1H), 5.12 (ddd, J = 18.4, 14.1, 1.0 Hz, 2H), 1.90−1.73 (m, 2H),
1.37 (s, 3H), 0.77 (t, J = 7.4 Hz, 3H). 13C NMR (126 MHz, CDCl3)
δ 148.5, 145.9, 130.2, 128.4, 123.4 (q, J = 3.9 Hz), 122.6 (q, J = 3.8
Hz), 112.7, 44.7, 33.4, 24.3, 8.8. 19F NMR (282 MHz, CDCl3) δ
−62.8. EI-MS: m/z 228.0 [M]+. HRMS (EI) m/z calcd for C13H15F3
[M]+: 228.1126. Found: 228.1129. Enantiomeric excess was
determined by chiral HPLC: Phenomenex Lux 5u Cellulose-3 (0.46
× 25 cm), CH3CN/H2O = 60/40, flow rate 0.7 mL/min, 214 nm,
retention times (min): 9.63 (minor) and 9.96 (major).
(R)-1′-Bromo-2′-(3-methylpent-1-en-3-yl)benzene (3xa). Color-
less oil; 54% yield; 3xa/4xa = 70/30; 22% ee. NMR experiments were
performed on the mixture of products, but only data of branched
product 3xa are given. 1H NMR (500 MHz, CDCl3) δ 7.57 (d, J = 7.8
Hz, 1H), 7.40 (d, J = 7.9 Hz, 1H), 7.26 (d, J = 7.3 Hz, 1H), 7.07 (dt, J
= 15.0, 7.6 Hz, 1H), 6.20 (ddd, J = 17.6, 10.7, 1.9 Hz, 1H), 5.10 (dd, J
= 10.7, 0.9 Hz, 1H), 4.93 (dd, J = 17.6, 0.8 Hz, 1H), 2.15 (dd, J =
14.5, 7.2 Hz, 2H), 1.49 (s, 3H), 0.71 (ddd, J = 7.4, 4.6, 1.2 Hz, 3H).
13C NMR (126 MHz, CDCl3) δ 146.3, 144.9, 132.6, 131.0, 130.2,
127.9, 127.1, 112.4, 46.2, 31.1, 25.6, 9.0. EI-MS: m/z 238.1 [M]+.
HRMS (EI) m/z calcd for C12H15Br [M]+: 238.0357. Found:
238.0360. The absolute configuration was assigned by analogy based
on 3wa through a similar stereochemical model. Enantiomeric excess
was determined by chiral HPLC: Phenomenex Lux 5u Cellulose-3
(0.46 × 25 cm), CH3CN/H2O = 70/30, flow rate 0.7 mL/min, 214
nm, retention times (min): 9.51 (minor) and 10.39 (major).
(R)-1′-(3-Methylpent-1-en-3-yl)naphthalene (3ya). Colorless oil;
55% yield; 3ya/4ya = 74/26; 86% ee. NMR experiments were
performed on the mixture of products, but only data of branched
product 3ya are given. 1H NMR (500 MHz, CDCl3) δ 8.41 (d, J = 8.4
Hz, 1H), 7.89−7.85 (m, 1H), 7.76 (d, J = 7.9 Hz, 1H), 7.51 (d, J =
7.3 Hz, 1H), 7.48 (dd, J = 3.6, 2.4 Hz, 1H), 7.45 (dd, J = 10.0, 4.9 Hz,
2H), 6.34 (dd, J = 17.6, 10.7 Hz, 1H), 5.10 (dd, J = 50.8, 14.2 Hz,
2H), 2.01 (dq, J = 14.4, 7.4 Hz, 2H), 1.59 (s, 3H), 0.69 (t, J = 7.4 Hz,
3H). 13C NMR (126 MHz, CDCl3) δ 148.9, 144.3, 142.3, 129.1,
127.7, 127.6, 125.1, 125.0, 124.8, 124.3, 112.0, 45.5, 32.8, 27.4, 9.0.
EI-MS: m/z 210.2 [M]+. HRMS (EI) m/z calcd for C16H18 [M]+:
210.1409. Found: 210.1415. The absolute configuration was assigned
by analogy based on 3wa through a similar stereochemical model.
Enantiomeric excess was determined by chiral HPLC: Chiralcel OD-
H column, n-hexane/i-PrOH = 100/0, flow rate 0.7 mL/min, 210 nm,
retention times (min): 16.47 (major) and 17.03 (minor).
(R)-1′-Methyl-3′-(3-methylpent-1-en-3-yl)benzene (3ta). Color-
less oil; 73% yield; 3ta/4ta = 75/25; 84% ee. NMR experiments were
performed on the mixture of products, but only data of branched
1
product 3ta are given. H NMR (500 MHz, CDCl3) δ 7.21 (dt, J =
7.9, 4.4 Hz, 2H), 7.13 (d, J = 5.8 Hz, 2H), 6.03 (dd, J = 17.5, 10.8 Hz,
1H), 5.13−5.02 (m, 2H), 2.19 (dd, J = 14.7, 7.3 Hz, 2H), 1.35 (s,
3H), 0.78 (t, J = 7.4 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ 147.5,
147.0, 127.9, 127.5, 126.4, 123.7, 111.6, 44.4, 33.4, 24.3, 21.7, 8.9. EI-
MS: m/z 174.2 [M]+. HRMS (EI) m/z calcd for C13H18 [M]+:
174.1409. Found: 174.1407. The absolute configuration was assigned
by analogy based on 3wa through a similar stereochemical model.
Enantiomeric excess was determined by chiral HPLC: Chiralcel OJ-H
column, n-hexane/i-PrOH = 100/0, flow rate 0.7 mL/min, 210 nm,
retention times (min): 7.75 (minor) and 9.45 (major).
(R)-1′-Bromo-3′-(3-methylpent-1-en-3-yl)benzene (3ua). Color-
less oil; 71% yield; 3ua/4ua = 79/21; 80% ee. NMR experiments
were performed on the mixture of products, but only data of branched
1
product 3ua are given. H NMR (500 MHz, CDCl3) δ 7.44 (s, 1H),
7.34−7.30 (m, 1H), 7.26−7.22 (m, 1H), 7.17 (d, J = 7.8 Hz, 1H),
5.97 (dd, J = 17.5, 10.8 Hz, 1H), 5.09 (dd, J = 42.1, 14.1 Hz, 2H),
1.78 (dtd, J = 21.1, 13.9, 7.4 Hz, 2H), 1.33 (s, 3H), 0.77 (t, J = 7.4 Hz,
3H). 13C NMR (126 MHz, CDCl3) δ 150.0, 146.0, 130.0, 129.5,
128.8, 125.4, 112.4, 44.6, 33.4, 24.3, 8.8. EI-MS: m/z 238.0 [M]+.
HRMS (EI) m/z calcd for C12H15Br [M]+: 238.0357. Found:
238.0355. The absolute configuration was assigned by analogy based
on 3wa through a similar stereochemical model. Enantiomeric excess
was determined by chiral HPLC: Chiralcel OJ-H column, n-hexane/i-
(R)-2′-(3-Methylpent-1-en-3-yl)naphthalene (3za). Colorless oil;
62% yield; 3za/4za = 81/19; 80% ee. NMR experiments were
performed on the mixture of products, but only data of branched
product 3za are given. 1H NMR (500 MHz, CDCl3) δ 7.83−7.79 (m,
3H), 7.74 (d, J = 1.6 Hz, 1H), 7.50−7.44 (m, 3H), 6.12 (dd, J = 17.5,
G
Organometallics XXXX, XXX, XXX−XXX