Organometallics
Article
Compound 3k. Following the general procedure, column
chromatography (50% CH2Cl2/hexanes) yielded 3k as a clear oil in
86% yield. 1H NMR and 13C NMR were consistent with the
literature.28
Compound 3l. Following the general procedure, column
chromatography (25% CH2Cl2/hexanes) yielded 3l as a clear oil in
75% yield. 1H NMR and 13C NMR were consistent with the
literature.27
Compound 3m. Following the general procedure, column
chromatography (37.5% CH2Cl2/hexanes) yielded 3m as a white
solid in 75% yield. 1H NMR (500 MHz, CDCl3): δ 7.71 (d, J = 8.0 Hz,
1H), 7.64 (d, J = 2.2 Hz, 1H), 7.23 (dd, J = 8.0, 2.2 Hz, 1H), 6.18 (q, J
= 6.9 Hz, 1H), 1.99 (d, J = 6.9 Hz, 3H), 1.36 (s, 6H), 1.35 (s, 6H). 13C
NMR (125 MHz, CDCl3): δ 151.5, 137.7, 137.4, 127.5, 126.9, 84.1,
47.1, 26.9, 25.0, 24.7. HRMS (ESI): m/z calculated for
C14H19BBrClO2 [M + H]+ 344.0460, found 344.0468.
Compound 3n. Following the general procedure and trapping,
column chromatography (0 to 37.5% CH2Cl2/hexanes) yielded 3n as a
clear oil in 58% yield over two steps. 1H NMR (500 MHz, CDCl3): δ
7.80 (d, J = 2.3 Hz, 1H), 7.67 (m, 2H), 7.59 (m, 2H), 7.41 (dd, J = 8.4,
2.3 Hz, 1H), 7.33 (m, 4H), 5.41 (q, J = 6.9 Hz, 1H), 1.52 (d, J = 6.9
Hz, 3H), 1.24 (s, 6H), 1.23 (s, 6H). 13C NMR (126 MHz, CDCl3): δ
147.5, 137.3, 133.0, 132.5, 132.0, 131.0, 128.7, 128.0, 127.2, 126.9,
126.6, 126.2, 125.3, 124.8, 119.5, 83.1, 42.9, 23.8, 23.8, 21.3. HRMS
(ESI): m/z calculated for C24H30NBrO2S [M + NH4]+ 488.1254,
found 488.1253.
(ASAP): m/z calculated for C17H26BBrO2 [M + NH4]+ 369.1584,
found 369.1584.
General Procedure for 1,3-Chlorine Migration. In a glovebox,
a round-bottom flask was charged with IHeptCuOMe (16.0 mg,
0.0225 mmol, 0.09 equiv) and toluene (2.5 mL). The flask was
brought out of the glovebox, placed in a preset oil bath at 45 °C, and
stirred for 5 min. The substrate (0.25 mmol, 1.0 equiv) was added via
syringe, followed immediately by addition of HBpin (72 μL, 0.5 mmol,
2.0 equiv). The reaction mixture was then put in an oil bath preset at
100 °C. After 1 h, the reaction mixture was concentrated. Stable benzyl
chlorides were purified by column chromatography.
Compound 6a. Following the general procedure, column
chromatography (25% CH2Cl2/hexanes) yielded 6a as a clear oil in
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69% yield. H NMR (500 MHz, CDCl3): δ 7.79 (d, J = 7.6 Hz, 1H),
7.68 (d, J = 7.9 Hz, 1H), 7.47 (t, J = 7.7 Hz, 1H), 7.27 (t, J = 7.9 Hz,
1H), 6.07 (q, J = 6.7 Hz, 1H), 1.81 (d, J = 6.7 Hz, 3H), 1.36 (s, 6H),
1.35 (s, 6H). 13C NMR (126 MHz, CDCl3): δ 149.2, 135.8, 131.5,
127.1, 125.9, 83.8, 57.3, 27.3, 24.9, 24.8. HRMS (EI): m/z calculated
for C14H20BClO2 [M + NH4]+ 283.1620, found 283.1621.
Compound 6b. Following the general procedure, column
chromatography (50% CH2Cl2/hexanes) yielded 6b as a yellow oil
in 68% yield. 1H NMR (500 MHz, CDCl3): δ 7.32 (t, J = 8.0 Hz, 1H),
7.15 (d, J = 7.8 Hz, 1H), 6.75 (d, J = 8.2 Hz, 1H), 5.21 (q, J = 6.8 Hz,
1H), 3.78 (s, 3H), 1.83 (d, J = 6.8 Hz, 3H), 1.40 (s, 6H), 1.39 (s, 6H).
13C NMR (126 MHz, CDCl3): δ 162.6, 147.8, 131.0, 118.1, 109.5,
84.1, 58.2, 55.7, 26.8, 24.8, 24.8. HRMS (ESI): m/z calculated for
C15H22BClO3 [M + NH4]+ 313.1726, found 313.1718.
Compound 3o. Following the general procedure, column
chromatography (37.5% CH2Cl2/hexanes) yielded 3o as a clear oil
in 56% yield. 1H NMR and 13C NMR were consistent with the
literature.28
Compound 6c. Following the general procedure, column
chromatography (50% CH2Cl2/hexanes) yielded 6c as a clear oil in
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88% yield. H NMR (500 MHz, CDCl3): δ 7.75 (d, J = 8.3 Hz, 1H),
Compound 3p. Following the general procedure and trapping,
column chromatography (0 to 37.5% CH2Cl2/hexanes) yielded 3p as a
white solid in 51% yield. 1H NMR (500 MHz, CDCl3): δ 8.02 (d, J =
2.2 Hz, 1H), 7.80 (s, 1H), 7.75 (d, J = 7.5, 1H), 7.64 (m, 6H), 7.42
(m, 5H), 7.32 (tt, J = 7.3, 1.3 Hz, 1H), 5.62 (q, J = 6.9 Hz, 1H), 1.68
(d, J = 6.9 Hz, 3H), 1.33 (s, 6H), 1.33 (s, 6H). 13C NMR (126 MHz,
CDCl3): δ 148.4, 140.8, 139.0, 134.7, 133.6, 133.6, 132.0, 129.8, 129.3,
129.0, 128.6, 127.9, 127.6, 127.2, 127.1, 127.1, 126.8, 126.2, 125.6,
83.8, 44.2, 24.9, 24.8, 22.4. HRMS (ESI): m/z calculated for
C30H31BO2S [M + NH4]+ 484.2481, found 484.2477.
7.23 (d, J = 2.5 Hz, 1H), 6.80 (dd, J = 8.4, 2.5 Hz, 1H), 6.08 (q, J =
6.7, 1H), 3.84 (s, 3H), 1.78 (d, J = 6.7 Hz, 3H), 1.34 (s, 6H), 1.32 (s,
6H). 13C NMR (126 MHz, CDCl3): δ 162.3, 151.7, 137.9, 112.6,
111.9, 57.2, 55.2, 27.5, 24.9, 24.8. HRMS (EI): m/z calculated for
C15H22BClO3 [M + NH4]+ 313.1726, found 313.1724.
Compound 6d. Following the general procedure, column
chromatography (25% CH2Cl2/hexanes) yielded 6d as a clear oil in
93% yield. 1H NMR (500 MHz, CDCl3): δ 7.6 (s, 1H), 7.57 (d, J = 8.0
Hz, 1H), 7.28 (d, J = 7.8 Hz, 1H), 6.02 (q, J = 6.8 Hz, 1H), 2.33 (s,
3H), 1.80 (d, J = 6.7 Hz, 3H), 1.36 (s, 6H), 1.34 (s, 6H). 13C NMR
(126 MHz, CDCl3): δ 146.4, 136.7, 136.2, 132.2, 125.9, 83.8, 57.2,
27.2, 24.9, 24.8, 20.93. HRMS (EI): m/z calculated for C15H22BClO2
[M + NH4]+ 297.1776, found 297.1768.
Compound 6e. Following the general procedure, column
chromatography (25% CH2Cl2/hexanes) yielded 6e as a white solid
in 48% yield. 1H NMR (500 MHz, CDCl3): δ 8.0 (s, 1H), 7.76 (d, J =
8.2 Hz, 1H), 7.69 (dd, J = 8.2, 2.0 Hz, 1H), 7.61 (d, J = 7.61 Hz, 2H),
7.43 (t, J = 7.48 Hz, 2H), 7.34 (t, J = 7.20 Hz, 1H), 6.74 (q, J = 6.7 Hz,
1H), 1.85 (d, J = 6.7 Hz, 3H), 1.37 (s, 6H), 1.36 (s, 6H). 13C NMR
(126 MHz, CDCl3): δ 148.3, 140.7, 139.9, 134.6, 130.2, 128.7, 127.3,
127.2, 126.5, 84.0, 57.1, 27.2, 24.9, 24.8. HRMS (EI): m/z calculated
for C20H24BClO2 [M + NH4]+ 359.1933, found 359.1931.
Compound 6f. Following the general procedure, column
chromatography (25% CH2Cl2/hexanes) yielded 6f as a white solid
in 77% yield. 1H NMR (500 MHz, CDCl3): δ 7.65 (d, J = 8.0 Hz, 1H),
7.59 (s, 1H), 7.18 (d, J = 8.0 Hz, 1H), 5.94 (q, J = 6.8 Hz, 1H), 1.70
(d, J = 6.8 Hz, 3H), 1.28 (s, 6H), 1.27 (s, 6H). 13C NMR (126 MHz,
CDCl3): δ 150.3, 136.8, 136.3, 126.3, 125.4, 83.0, 55.3, 26.2, 23.8,
23.75. HRMS (ASAP): m/z calculated for C14H19BCl2O2 [M + NH4]+
317.1230, found 317.1236.
Compound 3q. Following the general procedure, column
chromatography (25% CH2Cl2/hexanes) yielded 3q as a clear oil in
53% yield. 1H NMR and 13C NMR were consistent with the
literature.27
Compound 3r. Following the general procedure, column
chromatography (0 to 37.5% CH2Cl2/hexanes) yielded 3r as a clear
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oil in 31% yield. H NMR (500 MHz, CDCl3): δ 7.56 (d, J = 7.3 Hz,
1H), 7.21 (d, J = 7.5 Hz, 1H), 7.16 (t, J = 7.4 Hz, 1H), 6.24 (q, J = 7.4
Hz, 1H), 2.56 (s, 3H), 2.08 (d, J = 7.2 Hz, 3H), 1.37 (s, 12H). 13C
NMR (125 MHz, CDCl3): δ 145.5, 136.8, 134.6, 133.4, 127.3, 84.0,
49.0, 25.4, 24.9, 24.8, 21.0. HRMS (ASAP): m/z calculated for
C15H22BBrO2 [M + NH4]+ 341.1271, found 341.1260. For 3r and 3t,
carbons were difficult to assign based on 13C data alone.
Compound 3s. Following the general procedure, column
chromatography (0 to 37.5% CH2Cl2/hexanes) yielded 3s as a white
solid in 60% yield. 1H NMR (500 MHz, CDCl3): δ 7.43 (d, J = 7.9 Hz,
1H), 7.27 (t, J = 7.9 Hz, 1H), 7.05 (d, J = 7.9 Hz, 1H), 5.65 (q, J = 6.9
Hz, 1H), 2.42 (s, 3H), 2.04 (d, J = 6.9 Hz, 1H), 1.43 (s, 6H), 1.41 (s,
6H). 13C NMR (125 MHz, CDCl3): δ 147.3, 142.1, 129.8, 129.2,
123.1, 84.1, 49.3, 25.9, 25.1, 25.0, 22.3. HRMS (EI): m/z calculated for
C15H22BBrO2 [M + NH4]+ 342.1248, found 342.1252.
Compound 6g. Following the general procedure, column
chromatography (25% CH2Cl2/hexanes) yielded 6g as a clear oil in
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Compound 3t. Following the general procedure, column
chromatography (0 to 37.5% CH2Cl2/hexanes) yielded 3t as a clear
55% yield. H NMR (500 MHz, CDCl3): δ 7.92 (s, 1H), 7.90 (d, J =
7.9 Hz, 1H), 7.51 (d, J = 7.9 Hz, 1H), 6.06 (q, J = 6.7 Hz, 1H), 1.82
(d, J = 6.7 Hz, 3H), 1.37 (s, 6H), 1.36 (s, 6H). 13C NMR (126 MHz,
CDCl3): δ 150.1, 136.3, 133.2 (q, J = 32.3 Hz), 124.9 (q, J = 272.8
Hz), 123.6 (q, J = 3.82 Hz), 122.7 (q, J = 3.85 Hz), 84.4, 56.3, 27.2,
24.9, 24.8. HRMS (EI): m/z calculated for C15H19BF3O2 [M + H]+
334.1228, found 334.1222.
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oil in 20% yield. H NMR (500 MHz, CDCl3): δ 7.51 (d, J = 7.2 Hz,
1H), 7.20 (m, 2H), 6.07 (m, 1H), 2.81, (m, 2H), 2.10 (d, J = 7.1 Hz,
3H), 1.66 (sextet, J = 6.7, 2H), 1.39 (s, 6H), 1.37 (s, 6H), 1.02 (t, J =
7.3 Hz, 3H). 13C NMR (125 MHz, CDCl3): δ 145.1, 140.8, 133.3,
132.9, 127.2, 84.0, 48.4, 35.5, 35.49, 26.7, 24.9, 24.9, 24.8, 14.3. HRMS
H
Organometallics XXXX, XXX, XXX−XXX