8122
H. S. Knowles et al. / Tetrahedron 57 .2001) 8115±8124
30%), 318 135M1H1, 100), 282 110), 194 110), 161 110),
122 110), 105 120). Found: 35M1H1, 318.0893.
C17H1635ClNO3 requires for M1H1, 318.0897.
1424 1m), 1264 1s) cm21; dH 1270 MHz, CDCl3) 7.76±7.73
12H, m, ortho-H aromatics), 7.59±7.19 112H, m, aromatics),
6.65 11H, d, J7.5 Hz, NH), 5.14 11H, dt,J7.5 and 5.5 Hz,
NHCHCO), 3.79 13H, s, CO2CH3), 3.34 11H, dd, J14.0
and 5.5 Hz, CHAHBAr), 3.27 11H, dd, J14.0 and 5.5 Hz,
CHAHBAr); dC 167.5 MHz, CDCl3) 172.0 1CO2CH3), 166.8
1NCO), 140.6, 140.0, 134.8, 133.8 1CvCH), 131.8, 129.7,
128.7, 128.6, 127.3, 126.9, 126.8, 126.7 1CvCH), 53.5
1NHCHCO), 52.5 1CO2CH3), 37.5 1CH2Ar); m/z 1CI, NH3)
360 1M1H1, 100%), 238 110), 208 110), 167 110), 122 110),
105 110). Found: M1H1, 360.1589. C23H21NO3 requires for
M1H1, 360.1600.
3.10.4. Methyl N-benzoyl-3-chlorophenylalaninate 28.
White solid; mp91±94 8C; RF 0.7 1petroleum ether±ethyl
acetate, 1:1); nmax 1thin ®lm) 3419 1w), 3324 1m), 3061 1w),
2953 1m), 2929 1w), 1745 1vs), 1660 1vs), 1646 1vs), 1602
1m), 1578 1m), 1525 1s), 1484 1s), 1440 1m), 1360 1w), 1266
1m), 1216 1m) cm21; dH 1270 MHz, CDCl3) 7.93±7.72 12H,
m, aromatics), 7.60±7.00 16H, m, aromatics), 6.69 11H, br d,
J7.5 Hz, NH), 5.08 11H, dt, J7.5 and 5.5 Hz,
NHCHCO), 3.77 13H, s, CO2CH3), 3.28 11H, dd, J14.0
and 6.0 Hz, CHAHBAr), 3.19 11H, dd, J14.0 and 6.0 Hz,
CHAHBAr); dC 167.5 MHz, CDCl3) 171.8 1CO2CH3), 167.0
1PhCON), 138.0, 134.4, 133.6 1CvCH), 131.9, 129.8,
129.5, 128.7, 127.5, 127.4, 127.2, 127.0 1CvCH), 53.4
1NHCHCO), 52.6 1CO2CH3), 37.6 1CHCH2Ar); m/z 1CI,
NH3) 320 137M1H1, 30%), 318 135M1H1, 100), 284 120),
122 110), 105 110). Found: 35M1H1, 318.0897.
C17H1635ClNO3 requires for 35M1H1, 318.0897.
3.10.8. Methyl N-benzoyl-b-phenylphenylalaninate 32.
White solid; mp134±136 8C; RF 0.1 1dichloromethane±
toluene, 10:1); nmax 1CHCl3) 3437 1m), 3065 1w), 3031
1w), 2955 1w), 2247 1m), 1739 1s), 1666 1s), 1514 1s),
1484 1s), 1451 1m), 1360 1m), 1227 1m) cm21; dH
1270 MHz, CDCl3) 7.61±7.54 12H, m, ortho-H aromatics),
7.50±7.18 113H, m, aromatics), 6.40 11H, br d, J8.5 Hz,
NH), 5.60 11H, t, J8.5 Hz, NHCHCO), 4.60 11H, d,
J8.5 Hz, Ph2CH), 3.54 13H, s, CO2CH3); dC 167.5 MHz,
CDCl3) 171.3 1CO2CH3), 166.2 1CON), 140.0, 139.4
1CvCH), 128.5, 127.2, 127.1, 24.1 1CvCH), 52.8
1CO2CH3), 39.3 1NCH2CO); m/z 1CI, NH3) 360 1M1H1,
100%), 194 1100), 183 160), 167 140), 122 140), 105 170).
Found: M1H1, 360.1594. C23H21NO3 requires for M1H1,
360.1600.
3.10.5. Methyl N-benzoyl-4-chlorophenylalaninate 29.
White solid; mp100±102 8C 1lit.,2e 98±998C); RF 0.62
1petroleum ether±ethyl acetate, 1:1); nmax 1CHCl3) 3424
1m), 3361 1m), 3303 1m), 2951 1w), 1741 1s), 1653 1s),
1529 1m), 1444 1m), 1356 1w), 1298 1w) cm21; dH
1270 MHz, CDCl3) 7.74±7.71 12H, m, aromatics), 7.58±
7.19 15H, m, aromatics), 7.05 12H, d, J8.5 Hz,
ClCCHvCH or ClCCHvCH±CH), 6.66 11H, d,
J7.5 Hz, NH), 5.07 11H, dt, J7.5 and 5.5 Hz,
NHCHCO), 3.76 13H, s, CO2CH3), 3.29 11H, dd, J14.0
and 6.0 Hz, CHAHBAr), 3.18 11H, dd, J14.0 and 6.0 Hz,
CHAHBAr); dC 167.5 MHz, CDCl3) 171.8 1CO2CH3), 166.8
1PhCON), 133.6, 132.0, 131.8 1CvCH), 130.6, 128.6,
128.6, 127.1, 126.9 1CvCH), 53.4 1NHCHCO), 52.4
1CO2CH3), 37.1 1CH2Ar); m/z1CI, NH3) 320 137M1H1,
30%), 318 135M1H1, 100), 196 120), 122 110), 105 110),
49 110). Found: 35M1H1, 318.0896. C17H1635ClNO3
requires for 35M1H1, 318.0897.
3.10.9. Methyl N-benzoyl-29H-¯uoren-9-yl)glycinate 33.
Orange solid; mp154±156 8C; RF 0.5 1petroleum ether±
ethyl acetate, 1:1); nmax 1CHCl3) 3434 1w), 3023 1w),
1742 1m), 1665 1s), 1513 1s), 1483 1m), 1448 1w) cm21
;
dH 1270 MHz, CDCl3) 7.82±7.64 13H, m, aromatics),
7.48±7.23 110H, m, aromatics), 5.99 11H, d, J9.0 Hz,
NH), 5.70 11H, dd, J9.0 and 3.5 Hz, NHCHCO), 4.72
11H, d, J3.5 Hz, NHCHCHAr), 3.79 13H, s, CO2CH3);
dC 167.5 MHz, CDCl3) 171.5 1CO2CH3), 167.3 1CON),
142.8, 142.2, 141.1, 141.0, 133.8 1CvCH), 131.6, 128.4,
128.0, 127.6, 127.4, 126.8, 126.7, 124.8, 124.7, 120.2, 119.8
1CvCH), 54.0 1NHCHCO), 52.6 1CO2CH3), 49.2
1NHCHCHAr2); m/z 1CI, NH3) 358 1M1H1, 100%), 326
110), 236 110), 194 120), 162 110), 122 110), 105 120).
Found: M1H1, 358.1429. C23H19NO3 requires for
M1H1, 358.1443.
3.10.6. Methyl N-benzoyl-4-methylphenylalaninate 30.
RF 0.2 1petroleum ether±ethyl acetate, 3:111% toluene);
nmax 1thin ®lm) 3422 1br, w), 3337 1br, w), 2952 1w),
1744 1s), 1646 1s), 1579 1w), 1533 1s), 1520 1s), 1488 1m),
1442 1m), 1216 1m) cm21; dH 1270 MHz, CDCl3) 7.75±7.72
12H, m, aromatics), 7.60±7.26 13H, m, aromatics), 7.10 12H,
d, J8.0 Hz, 2£CH3C±CHvCH), 7.02 12H, d,J8.0 Hz,
2£CH3±CHvCH), 5.07 11H, dt,J7.5 and 5.5 Hz,
NHCHCO), 3.77 13H, s, CO2CH3), 3.26 11H, dd, J14.0
and 5.5 Hz, CHAHBAr), 3.19 11H, dd, J14.0 and 5.5 Hz,
CHAHBAr), 2.32 13H, s, CH3CvCH); dC 167.5 MHz,
CDCl3) 172.3 1CO2CH3), 167.0 1CON), 137.0, 134.1,
132.8 1CvCH), 132.0, 129.2, 128.9, 128.5, 127.2
1CvCH), 53.6 1NHCHCO), 52.7 1CO2CH3), 37.6
1CH2Ar); m/z 1CI, NH3) 298 1M1H1, 100%), 194 110),
176 120), 105 120). Found: M1H1, 298.1439. C18H19NO3
requires for M1H1, 298.1443.
3.11. Photolysis of dimethyl 2-2N-benzoylamino)-
malonate 35
A mixture of malonate 3537 14.55 g, 18.1 mmol), di-tert-
butyl peroxide 15.29 g, 6.6 ml, 36.2 mmol) and toluene
18.33 g, 9.6 ml, 90.5 mmol) in benzene 1184 ml) was
photolysed for 12 h using a 400 W lamp. After evaporation
in vacuo, the crude product was isolated as an orange oil
18.13 g). A sample 10.98 g, 12.0% of the crude mass) was
puri®ed by column chromatography 1silica; petroleum
ether±ethyl acetate, 2:1) to afford 1,2-diphenylethane
10.211 g), methyl 2-1N-benzoylamino)-2-benzylmalonate
36 [0.098 g, 0.817 g upon scale up, 13%, 158% based on
recovered malonate)], methyl N-benzoylphenylalaninate
11a [0.017 g, 0.142 g scaled, 3%, 112%)] and starting
malonate 35 10.42 g, scaled upto 3.53 g, 78%).
3.10.7. Methyl N-benzoyl-4-phenylphenylalaninate 31.
White solid; mp130±132 8C; RF 0.5 1petroleum ether±
ethyl acetate, 3:1); nmax 1CHCl3) 3423 1w), 3053 1s), 2985
1m), 1741 1m), 1662 1m), 1542 1m), 1485 1m), 1440 1m),