Benzylic Manganese Halides, Sulfonates, and Phosphates
J . Org. Chem., Vol. 65, No. 8, 2000 2329
chromatography (ethyl acetate/hexanes) afforded 2m in 56%
isolated yield.
drous MgSO4, and concentrated using a rotary evaporator.
Flash column chromatography (ethyl acetate/hexanes) afforded
the corresponding coupling product.
Eth yl 4-Ben zylben zoa te (2m ). Pale-yellow oil. 1H NMR
(CDCl3): δ 8.05-7.20 (m, 9H), 4.41 (q, J ) 7.15 Hz, 2H),
4.06 (s, 2H), 1.42 (t, J ) 7.15 Hz, 3H). 13C NMR: δ 166.42,
146.27, 140.06, 129.68, 128.82, 128.79, 128.49, 128.34, 126.25,
60.68, 41.77, 14.22. HRMS calcd for C16H16O2 240.1150 found
240.1151.
1-(3,5-Dim eth oxyp h en yl)-2-h yd r oxytr id eca n e (4a ). 1H
NMR (CDCl3): δ 6.37-6.35 (m, 3H), 3.78 (s, 7H), 2.80, 2.75
(dd, J ) 3.82 Hz, 3.81 Hz, 1H), 2.58, 2.54 (dd, J ) 8.59 Hz,
8.58 Hz, 1H), 1.60 (br s, 1H), 1.52-1.26 (m, 20H), 0.88 (t, J )
5.96 Hz, 3H). 13C NMR: δ 160.89, 140.99, 107.30, 98.38, 72.48,
55.24, 44.36, 36.84, 31.89, 29.64, 29.61, 29.33, 25.75, 22.66,
14.09.
Eth yl 4-(4′Br om oben zyl)ben zoa te (2n ). Pale-yellow oil.
1H NMR (CDCl3): δ 8.00-7.03 (m, 8H), 4.37 (q, J ) 7.15 Hz,
2H), 3.98 (s, 2H), 1.39 (t, J ) 7.15 Hz, 3H). 13C NMR: δ 166.39,
145.56, 139.10, 131.60, 130.58, 129.99, 129.81, 129.00, 128.78,
128.63, 120.19, 60.80, 41.18, 14.27. EIMS m/z (relative inten-
sity): 319 (M+, 34).
1-(3,5-Dim eth oxyp h en yl)-2-h yd r oxyp en ta d eca n e (4b).
1H NMR (CDCl3): δ 6.38-6.35 (m, 3H), 3.78 (s, 7H), 2.80,
2.75 (dd, J ) 4.06 Hz, 4.05 Hz, 1H), 2.59, 2.54 (dd, J ) 8.58
Hz, 8.82 Hz, 1H), 1.62 (s, 1H), 1.53-1.26 (m, 24H). 0.89 (t,
J ) 6.20 Hz, 3H). 13C NMR: δ 160.87, 140.98, 107.28, 98.36,
72.47, 55.21, 44.36, 36.84, 31.89, 29.64, 29.33, 25.74, 22.65,
14.08.
6. Typ ica l P r oced u r e for th e Cr oss-Cou p lin g Rea c-
tion s of Ben zyl Ma n ga n ese Su lfon a tes. Benzyl mesylate10
(9 mmol) was added via syringe to a slurry of active manganese
(10 mmol) being stirred in THF (10 mL) at room temperature.
The resulting mixture was stirred at room temperature for
20 min. The reaction was monitored by gas chromatography.
After the completion of the oxidative addition, the mixture was
cooled to 0 °C. 1,2-Dibromoethane was added to the mixture
at this temperature, and the mixture was stirred for 5 min.
Benzoyl chloride was added to the resulting mixture at room
temperature. After being stirred for 30 min, the mixture was
quenched with 3 M HCl solution and extracted with diethyl
ether. The combined organic layers were washed with NaH-
CO3, Na2S2O3, and brine, dried over anhydrous MgSO4, and
concentrated using a rotary evaporator. Flash column chro-
matography (ethyl acetate/hexanes) afforded the corresponding
ketones.
3-(4′-Br om op h en yl)-2-p h en ylp r op a n -2-ol (3j). Pale-
brown oil. 1H NMR (CDCl3): δ 7.41-6.85 (m, 9H), 3.04 (q,
J ) 13.50 Hz, 2H), 1.59 (s, 3H). 13C NMR: δ 147.00, 135.77,
132.20, 130.90, 128.04, 126.74, 124.88, 120.56, 74.33, 49.78,
29.18.
2-(4′-Ch lor op h en yl)-1-p h en ylet h a n -1-ol (3k ). Pale-
yellow solid; mp 55-56 °C. 1H NMR (CDCl3): δ 7.36-7.08
(m, 9H), 4.84 (t, J ) 6.60 Hz, 1H), 2.99 (d, J ) 6.90 Hz, 2H),
2.14 (d, J ) 4.20 Hz, 1H). 13C NMR: δ 143.45, 136.41, 132.26,
130.80, 128.39, 127.67, 125.81, 75.13, 45.03.
1-(3,5-Dim et h oxyp h en yl)-p en t a d eca n -2-on e (4c). 1H
NMR (CDCl3): δ 6.35 (br s, 3H), 3.78 (br s, 6H), 3.60 (s, 2H),
2.44 (t, J ) 7.39 Hz, 2H), 1.53 (br s, 2H), 1.25-1.23 (m, 20H),
0.88 (t, J ) 6.90 Hz, 3H). 13C NMR: δ 208.46, 160.93, 136.49,
107.28, 98.93, 55.25, 50.42, 41.76, 31.88, 29.59, 29.42, 29.32,
29.05, 23.70, 22.65, 14.06.
1-(3,5-Dim et h oxyp h en yl)-h ep t a d eca n -2-on e (4d ). 1H
NMR (CDCl3): δ 6.35 (br s, 3H), 3.78 (s, 6H), 3.59 (s, 2H), 2.43
(t, J ) 7.39 Hz, 2H), 1.59 (br s, 2H), 1.25-1.23 (m, 24H), 0.88
(t, J ) 5.72 Hz, 3H). 13C NMR: δ 208.45, 160.91, 136.49,
107.37, 98.93, 55.25, 50.42, 41.76, 31.88, 29.64, 29.61, 29.55,
29.42, 29.32. 29.07, 23.70, 22.65, 14.08.
2-(3,5-Dim et h oxyp h en yl)-1-p h en ylet h a n -1-ol (5). 1H
NMR (CDCl3): δ 7.28-7.26 (m, 5H), 6.36 (br s, 3H), 4.91, 4.88
(dd, J ) 4.76 Hz, 4.77 Hz, 1H), 3.76 (s, 6H), 3.03-2.88 (m,
2H), 2.09 (br s, 1H). 13C NMR: δ 160.80, 143.70, 140.25,
128.75, 127.57, 125.87, 107.36, 98.67, 75.03, 55.24, 55.21,
46.40.
2-(3,5-Dim eth oxyp h en yl)-1-(3′-m eth oxyp h en yl)eth a n -
1-ol (6). 1H NMR (CDCl3): δ 7.29-6.81 (m, 4H), 6.36 (br s,
3H), 4.86, 4.83 (dd, J ) 4.77 Hz, 5.01 Hz, 1H), 3.80, 3.75 (ss,
9H), 2.96-2.91 (m, 2H), 2.35 (br s, 1H). 13C NMR: δ 160.62,
159.52, 145.43, 140.22, 129.25, 118.10, 112.99, 111.14, 107.27,
98.52, 74.81, 55.08, 46.20, 3509 (br), 2939, 2836, 1598, 1463,
3-(4′-Ch lor op h en yl)-2-p h en ylp r op a n -2-ol (3l). Pale-
yellow oil. 1H NMR (CDCl3): δ 7.41-6.90 (m, 9H), 3.05 (q,
J ) 13.50 Hz, 2H), 1.89 (br s, 1H), 1.58 (s, 3H). 13C NMR: δ
147.04, 135.24, 132.42, 131.81, 128.05, 127.98, 126.76, 124.89,
74.40, 49.74, 29.23. HRFAB calcd for C15H15ClO 246.0811,
found (M + Li)+ 253.0969.
1262, 1067, 832 cm-1
.
2-(3,5-Dim eth oxyp h en yl)-1-(4′-m eth oxyp h en yl)eth a n -
1-ol (7). 1H NMR (CDCl3): δ 7.27, 6.88 (dd, J ) 11.45 Hz, 8.58
Hz, 4H), 6.35 (br s, 3H), 4.83 (t, J ) 7.39 Hz, 1H), 3.80, 3.75
(ss, 9H), 2.94-2.91 (m, 2H), 2.17 (br s, 1H). 13C NMR: δ 160.70,
158.95, 140.41, 135.91, 127.08, 113.66, 107.31, 98.54, 74.62,
55.15, 46.27.
2-(3′-Tr iflu or om eth ylp h en yl)-1-p h en yleth a n -1-ol (3m ).
1
Pale-yellow oil. H NMR (CDCl3): δ 7.52-7.31 (m, 9H), 4.89,
1-(3,4-Dim et h oxyp h en yl)-2-(3′,5′-d im et h oxyp h en yl)-
1
4.87 (dd, J ) 5.96, 5.72 Hz, 1H), 3.08 (m, 2H), 2.14 (s, 1H).
13C NMR: δ 143.36, 139.00, 132.94, 128.62, 128.44, 127.80,
126.19 (q), 125.80, 123.27 (q), 75.05, 45.41. HRFAB calcd for
eth a n -1-ol (8). H NMR (CDCl3): δ 6.90-6.80 (m, 3H), 6.34
(br s, 3H), 4.83, 4.81 (dd, J ) 5.40 Hz, 5.49 Hz, 1H), 3.86, 3.73
(ss, 12H), 2.94-2.90 (m, 2H), 2.16 (br s, 1H). 13C NMR: δ
160.73, 148.85, 148.31, 140.32, 136.39, 118.04, 110.79, 108.94,
107.73, 98.52, 74.81, 55.82, 55.75, 55.15, 46.33.
C
15H13F3O 266.0918, found (M + Li)+ 273.1076.
2-(2′-Ch lor o-4′-flu or op h en yl)-1-p h en yleth a n -1-ol (3n ).
Pale-yellow solid; mp 64-66 °C. 1H NMR (CDCl3):
δ
1-(4-Ben zyloxy-3-m et h oxyp h en yl)-2-(3′,5′-d im et h oxy-
p h en yl)eth a n -1-ol (9). 1H NMR (CDCl3): δ 7.46-6.78 (m,
8H), 6.35 (br s, 3H), 5.14 (s, 2H), 4.79 (t, J ) 6.68 Hz, 1H),
3.86, 3.72 (ss, 9H), 2.92 (d, J ) 6.44 Hz, 2H), 2.45 (br s, 1H).
13C NMR: δ 160.49, 149.33, 147.18, 140.25, 136.94, 128.27,
127.57, 127.03, 117.88, 113.50, 109.42, 107.21, 98.33, 74.61,
70.72, 55.69, 54.96, 46.08.
7.36-6.86 (m, 8H), 4.96, 4.93 (dd, J ) 5.25, 5.01 Hz, 1H), 3.18-
3.03 (m, 2H), 2.39 (br s, 1H). 13C NMR: δ 162.87, 159.58,
143.62, 134.66, 134.53, 132.81, 132.69, 131.81, 131.76, 128.36,
127.64, 125.64, 116.76, 116.44, 113.83, 113.56, 73.30, 42.68.
HRFAB calcd for C14H12ClFO 250.0561, found (M + Li)+
257.0729.
2-(3′-Meth oxyp h en yl)-1-p h en yleth a n -1-ol (3p ). 1H NMR
(CDCl3): δ 7.39-6.75 (m, 8H), 4.91, 4.88 (dd, J ) 5.48, 5.45
Hz, 1H), 3.78 (s, 3H), 3.03, 3.00 (dd, J ) 3.10, 5.96 Hz, 2H),
2.24 (s, 1H). 13C NMR: δ 159.50, 143.70, 139.52, 129.33,
128.27, 127.45, 125.81, 121.72, 114.95, 111.98, 75.06, 54.99,
45.98.
7. Typ ica l P r oced u r e for th e Cou p lin g Rea ction of 1f
w ith Ald eh yd es a n d Acid Ch lor id es (4a -4d , 5-9). Ben-
zylic manganese reagent was prepared as before. To the
resulting benzylic manganese reagent was added the aldehyde
(or acid chloride) at room temperature. After being stirred for
1 h, the mixture was quenched with 3 M HCl solution and
extracted with diethyl ether. The combined organic layers were
washed with NaHCO3, Na2S2O3, and brine, dried over anhy-
8. Typ ica l P r oced u r e for th e Hom ocou p lin g P r od u cts
(10a -c). To a slurry of Mn* was added m-cyanobenzyl bromide
at room temperature, and the resulting mixture was stirred
at this temperature for 20 min. The oxidative addition was
monitored by TLC and/or gas chromatography. The mixture
was quenched with 3 M HCl solution and extracted with ethyl
acetate. The organic layer was washed with saturated Na2-
HCO3 and solutions of NaCl followed by drying over anhydrous
MgSO4. Recrystallization with ethanol gave 1,2-di-(m-cyano-
phenyl)ethane in 90% isolated yield.
1,2-Di-(m -cya n op h en yl)eth a n e (10a ). Pale-brown solid;
1
mp 159-161 °C. H NMR (CDCl3): δ 7.53-7.33 (m, 4H), 2.97
(s, 2H). 13C NMR: δ 141.85, 132.97, 131.88, 130.10, 129.23,
118.72, 112.51, 36.77.