The Journal of Organic Chemistry
Article
1204 (w), 1162 (w), 1049 (s), 1025 (s), 974 (m), 925 (w), 861 (m),
793 (m), 754 (s), 700 (m), 679 (w), 588 (m), 511 (w); 1H NMR (400
MHz, CDCl3) δ 1.37 (t, J = 7.0 Hz, 3H), 1.37 (t, J = 7.0 Hz, 3H), 1.84
(d, J = 14.3 Hz, 3H), 2.06 (d, J = 1.1 Hz, 3H), 2.50 (dddd, J = 15.2,
12.7, 10.5, 5.0 Hz, 1H), 2.74 (ddt, J = 15.2, 10.0, 5.3 Hz, 1H), 2.89
(ddd, J = 16.7, 10.0, 5.0 Hz, 1H), 2.97 (ddd, J = 16.7, 10.5, 5.3 Hz,
1H), 4.20−4.32 (m, 4H), 7.31−7.38 (m, 1H), 7.39−7.44 (m, 4H),
7.50 (q, J = 1.1 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 13.1, 16.3,
16.4, 20.2, 30.6, 31.7 (d, J = 8.0 Hz), 64.3, 64.3, 89.4 (d, J = 149.0 Hz),
128.4, 128.7, 129.7, 135.5, 136.6, 139.3, 199.5; 31P NMR (162 MHz,
CDCl3) δ 16.6; MS (ES+, Ar) m/z (rel intensity) 386 ([MH + 2]+, 4),
385 ([MH + 1]+, 22), 384 (MH+, 100), 359 (13), 338 (12), 337 (36),
266 (30), 238 (12), 201 (25), 200 (11), 199 (50), 179 (14); HRMS
(ES+, Ar) calcd for C18H27NO6P (MH+) 384.1576, found 384.1557;
1H), 3.48 (ddd, J = 18.2, 11.2, 4.4 Hz, 1H), 4.16−4.28 (m, 2H), 4.31−
4.41 (m, 2H), 7.32 (t, J = 7.9 Hz, 1H), 7.67 (ddd, J = 7.9, 1.8, 1.0 Hz,
1H), 7.86 (ddd collapsed to dt, J = 7.9, 1.0 Hz, 1H), 8.06 (dd
collapsed to t, J = 1.4 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 2.9 (d,
J = 6.0 Hz), 3.9 (d, J = 3.0 Hz), 16.5 (d, J = 6.0 Hz), 16.6 (d, J = 6.0
Hz), 18.2, 25.8, 33.8 (d, J = 2.0 Hz), 63.7 (d, J = 8.0 Hz), 64.8 (d, J =
6.0 Hz), 92.9 (d, J = 156.0 Hz), 123.1, 126.8, 130.4, 131.1, 136.3,
138.3, 197.1; 31P NMR (162 MHz, CDCl3) δ 15.8; MS (ES+, Ar) m/z
(rel intensity) 451 ([MH + 3]+, 24), 450 ([MH + 2]+, 88), 449 ([MH
+ 1]+, 25), 448 (MH+, 100), 404 (22), 403 (93), 402 (27), 401 (81),
265 (30), 263 (40); HRMS (ES+, Ar) calcd for C17H24NO6PBr (MH+)
448.0525, found 448.0523; [α]25D = −2.10° (c = 1.00, CHCl3); HPLC
Chiralcel OD-H (pet ether/i-PrOH = 95/5, flow rate 0.5 mL/min, λ =
230 nm), tR (major) = 24.1 min, tR (minor) = 31.8 min; 92% ee.
Diethyl 1-(3-bromophenyl)-4-nitro-1-oxotridecan-4-ylphospho-
nate (7d). Colorless oil; Yield 105 mg, 98%; IR (neat, cm−1) 3064
(m), 2930 (vs), 2860 (vs), 1692 (vs), 1548 (vs), 1467 (s), 1444 (s),
1393 (w), 1369 (w), 1340 (w), 1263 (m), 1207 (m), 1163 (m), 1096
(m), 1067 (s), 951 (m), 904 (w), 864 (w), 790 (s), 761 (s), 739 (s),
700 (m), 682 (m), 566 (m); 1H NMR (400 MHz, CDCl3) δ 0.87 (t, J
= 6.9 Hz, 3H), 1.18−1.32 (m, 13H), 1.35 (t, J = 7.1 Hz, 3H), 1.37 (t, J
= 7.1 Hz, 3H), 1.41−1.54 (m, 1H), 2.05−2.20 (m, 1H), 2.23−2.37 (m,
1H), 2.46 (dtd, J = 15.4, 10.0, 5.4 Hz, 1H), 2.72 (dtd, J = 15.4, 10.0,
5.4 Hz, 1H), 3.26 (ABqdd, J = 17.9, 10.0, 5.4 Hz, 2H), 4.11−4.35 (m,
4H), 7.34 (t, J = 7.9 Hz, 1H), 7.69 (ddd, J = 7.9, 1.8, 1.0 Hz, 1H), 7.89
(ddd collapsed to dt, J = 7.9, 1.0 Hz, 1H) 8.08 (dd collapsed to dt, J =
1.4 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 14.2, 16.5 (d, J = 5.0
Hz), 16.6 (d, J = 5.0 Hz), 22.8, 23.6, 23.7, 28.1, 29.3 (d, J = 3.0 Hz),
29.6, 29.6, 32.0, 34.0 (d, J = 4.0 Hz), 36.4, 64.0 (d, J = 7.0 Hz), 64.7 (d,
J = 7.0 Hz), 93.2 (d, J = 150.0 Hz), 123.2, 126.8, 130.4, 131.2, 136.3,
138.4, 197.1; 31P NMR (162 MHz, CDCl3) δ 16.2; MS (ES+, Ar) m/z
(rel intensity) 559 ([MNa + 3]+, 27), 558 ([MNa + 2]+, 100), 557
([MNa + 1]+, 28), 556 (MNa+, 100); HRMS (ES+, Ar) calcd for
[α]25 = −19.79° (c = 1.00, CHCl3); HPLC Chiralcel OD-H (pet
D
ether/i-PrOH = 95/5, flow rate 1.0 mL/min, λ = 280 nm), tR (major)
= 18.0 min, tR (minor) = 21.2 min; 90% ee.
Diethyl 6-(3-bromophenyl)-3-nitro-6-oxohexan-3-ylphosphonate
(7a). Colorless oil; Yield 84 mg, 96%; IR (neat, cm−1) 2984 (m), 2942
(w), 1692 (s), 1546 (vs), 1442 (w), 1421 (w), 1257 (s), 1207 (w),
1163 (w), 1049 (vs), 1023 (vs), 976 (m), 791 (m), 757 (m), 681 (m);
1H NMR (400 MHz, CDCl3) δ 0.97 (t, J = 7.4 Hz, 3H), 1.29 (t, J =
7.1 Hz, 3H), 1.31 (t, J = 7.1 Hz, 3H), 2.16 (ddq, J = 14.8, 11.8, 7.4 Hz,
1H), 2.31 (ddq, J = 14.8, 12.2, 7.4 Hz, 1H), 2.41 (dtd, J = 15.5, 10.8,
4.9 Hz, 1H), 2.65 (dtd, J = 15.5, 10.8, 4.9 Hz, 1H), 3.17, 3.25 (ABqdd,
J = 15.9, 10.9, 4.9 Hz, 2H), 4.10−4.28 (m, 4H), 7.28 (t, J = 7.9 Hz,
1H), 7.62 (ddd, J = 7.9, 1.8, 1.0 Hz, 1H), 7.83 (ddd collapsed to dt, J =
7.9, 1.4 Hz, 1H), 8.02 (dd collapsed to t, J = 1.6 Hz, 1H); 13C NMR
(100 MHz, CDCl3) δ 8.4 (d, J = 7.0 Hz), 16.5 (d, J = 5.0 Hz), 16.5 (d,
J = 5.0 Hz), 27.7, 29.7, 33.9 (d, J = 4.0 Hz), 63.9 (d, J = 7.0 Hz), 64.7
(d, J = 7.0 Hz), 93.5 (d, J = 150.0 Hz), 123.2, 126.8, 130.4, 131.2,
136.3, 138.3, 197.0; 31P NMR (162 MHz, CDCl3) δ 16.2; MS (ES+,
Ar) m/z (rel intensity) 439 ([MH + 3]+, 20), 438 ([MH + 2]+, 97),
437 ([MH + 1]+, 20), 436 (MH+, 100), 391 (35), 390 (34), 253 (19),
251 (18), 193 (23); HRMS (ES+, Ar) calcd for C16H24NO6BrP (MH+)
436.0525, found 436.0532; [α]25D = −9.06° (c = 1.00, CHCl3); HPLC
Chiralcel OD-H (pet ether/i-PrOH = 95/5, flow rate 0.5 mL/min, λ =
216 nm), tR (major) = 24.6 min, tR (minor) = 26.3 min; 92% ee.
Diethyl 1-(3-bromophenyl)-4-nitro-1-oxoheptan-4-ylphospho-
nate (7b). Colorless oil; Yield 87 mg, 97%; IR (neat, cm−1) 2973
(s), 2934 (m), 2876 (w), 1692 (s), 1547 (s), 1468 (w), 1443 (w),
1422 (w), 1338 (vw), 1295 (w), 1255 (s), 1208 (m), 1163 (w), 1096
C23H37NO6PBrNa (MNa+) 556.1434, found 556.1434; [α]25
=
D
−6.72° (c = 1.00, CHCl3); HPLC Chiralcel OD-H (pet ether/i-PrOH
=95/5, flow rate 0.5 mL/min, λ = 230 nm), tR (major) = 15.3 min, tR
(minor) = 18.3 min; 95% ee.
Ethyl 8-(3-bromophenyl)-5-(diethoxyphosphoryl)-5-nitro-8-ox-
ooctanoate (7e). Colorless oil; Yield 99 mg, 95%; IR (neat, cm−1)
3062 (m), 2983 (vs), 2939 (vs), 1727 (vs), 1697 (vs), 1548 (vs), 1477
(w), 1445 (w), 1420 (w), 1338 (vw), 1296 (w), 1261 (m), 1184 (m),
1163 (m), 1096 (m), 1047 (s), 1028 (s), 976 (w), 788 (s), 739 (vs),
703 (s), 684 (m), 563 (m); 1H NMR (400 MHz, CDCl3) δ 1.19 (t, J =
7.1 Hz, 3H), 1.29 (t, J = 7.3 Hz, 3H), 1.31 (t, J = 7.3 Hz, 3H), 1.52−
1.65 (m, 1H), 1.68−1.82 (m, 1H), 2.12−2.34 (m, 2H), 2.29 (t, J = 7.0
Hz, 2H), 2.42−2.54 (m, 1H), 2.59−2.73 (m, 1H), 3.22 (ABqdd, J =
9.3, 5.9, 3.0 Hz, 2H), 4.07 (q, J = 7.1 Hz, 2H), 4.12−4.27 (m, 4H),
7.28 (t, J = 7.9 Hz, 1H), 7.63 (ddd, J = 7.9, 1.8, 1.0 Hz, 1H), 7.83 (ddd
collapsed to dt, J = 7.9, 1.0 Hz, 1H), 8.04 (dd collapsed to t, J = 1.4
Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 14.4, 16.5 (d, J = 5.0 Hz),
16.6 (d, J = 5.0 Hz), 19.2, 19.3, 27.9, 33.7, 34.9, 60.8, 64.2 (d, J = 8.0
Hz), 64.8 (d, J = 6.0 Hz), 92.8 (d, J = 149.0 Hz), 123.2, 126.8, 130.4,
131.3, 136.3, 138.3, 172.7, 196.3; 31P NMR (162 MHz, CDCl3) δ 15.7;
MS (ES+, Ar) m/z (rel intensity) 525 ([MH + 3]+, 25), 524 ([MH +
2]+, 100), 523 ([MH + 1]+, 25), 522 (MH+, 100), 478 (40), 477 (36),
476 (40), 475 (30), 431 (20), 429 (20), 301 (31); HRMS (ES+, Ar)
1
(w), 1048 (vs), 1026 (vs), 976 (s), 855 (vw), 790 (m), 765 (m); H
NMR (400 MHz, CDCl3) δ 0.95 (t, J = 7.3 Hz, 3H), 1.35 (t, J = 7.1
Hz, 3H), 1.37 (t, J = 7.1 Hz, 3H), 1.42−1.58 (m, 1H), 2.09−2.22 (m,
1H), 2.21−2.34 (m, 1H), 2.47 (dtd, J = 15.5, 10.2, 5.2 Hz, 1H), 2.71
(dtd, J = 15.5, 10.2, 5.2 Hz, 1H), 3.22, 3.29 (ABqdd, J = 17.9, 10.2, 5.2
Hz, 2H), 4.16−4.35 (m, 4H), 7.34 (t, J = 7.9 Hz, 1H), 7.68 (ddd, J =
7.9, 1.7, 0.9 Hz, 1H), 7.88 (ddd collapsed to dt, J = 7.9, 1.3 Hz, 1H),
8.08 (dd collapsed to t, J = 1.3 Hz, 1H); 13C NMR (100 MHz, CDCl3)
δ 14.1, 16.5 (d, J = 5.0 Hz), 16.6 (d, J = 5.0 Hz), 17.2 (d, J = 7.0 Hz),
28.1, 34.0 (d, J = 4.0 Hz), 38.3, 64.0 (d, J = 7.0 Hz), 64.7 (d, J = 7.0
Hz), 93.2 (d, J = 150.0 Hz), 123.2, 126.8, 130.4, 131.2, 136.3, 138.3,
197.0; 31P NMR (162 MHz, CDCl3) δ 16.1; MS (ES+, Ar) m/z (rel
intensity) 453 ([MH + 3]+, 21), 452 ([MH + 2]+, 99), 451 ([MH +
1]+, 22), 450 (MH+, 100), 406 (11), 405 (49), 404 (11), 403 (54), 377
(9), 375 (9), 359 (10), 357 (11), 267 (22), 265 (22), 207 (23);
HRMS (ES+, Ar) calcd for C17H26NO6PBr (MH+) 450.0681, found
450.0684; [α]25D = −9.70° (c = 1.00, CHCl3); HPLC Chiralcel OD-H
(pet ether/i-PrOH = 95/5, flow rate 0.5 mL/min, λ = 216 nm), tR
(major) = 20.2 min, tR (minor) = 23.0 min; 96% ee.
Diethyl 4-(3-bromophenyl)-1-cyclopropyl-1-nitro-4-oxobutyl-
phosphonate (7c). Colorless oil; Yield 84 mg, 94%; IR (neat,
cm−1) 3065 (m), 2983 (vs), 2931 (s), 2913 (s), 2871 (m), 1691 (vs),
1547 (vs), 1474 (m), 1441 (s), 1335 (w), 1256 (s), 1210 (m), 1163
(m), 1097 (m), 1047 (s), 974 (m), 842 (w), 788 (s), 758 (s), 737 (m),
603 (m), 567 (s); 1H NMR (400 MHz, CDCl3) δ 0.62−0.71 (m, 2H),
0.72−0.82 (m, 2H), 1.34 (t, J = 7.4 Hz, 3H), 1.39 (t, J = 7.1 Hz, 3H),
1.74 (sextet, J = 7.1 Hz, 1H), 2.23 (ddt, J = 15.4, 11.1, 4.4 Hz, 1H),
2.41 (dtd, J = 15.4, 11.2, 4.4 Hz, 1H), 3.10 (ddd, J = 18.2, 11.1, 4.4 Hz,
calcd for C20H30NO8PBr (MH+) 522.0892, found 522.0872; [α]25
=
D
−4.30° (c = 1.00, CHCl3); HPLC Chiralpack IA (pet ether/i-PrOH =
80/20, flow rate 1.0 mL/min, λ = 250 nm), tR (major) = 10.1 min, tR
(minor) = 8.4 min; 91% ee.
Diethyl 6-(3-bromophenyl)-3-nitro-6-oxo-1-phenylhexan-3-yl-
phosphonate (7f). Colorless oil; Yield 100 mg, 98%; IR (neat,
cm−1) 3063 (w), 3027 (w), 2982 (s), 2934 (m), 2870 (w), 1691 (vs),
1548 (vs), 1497 (w), 1442 (m), 1421 (m), 1393 (w), 1338 (w), 1257
(vs), 1209 (s), 1163 (w), 1096 (w), 1044 (vs), 974 (s), 791 (m), 756
1
(s), 738 (s), 701 (s); H NMR (400 MHz, CDCl3) δ 1.29 (t, J = 7.1
Hz, 3H), 1.32 (t, J = 7.1 Hz, 3H), 2.32−2.45 (m, 1H), 2.46−2.64 (m,
3H), 2.65−2.79 (m, 2H), 3.22 (ABqdd, J = 18.0, 10.4, 5.0 Hz, 2H),
4.12−4.30 (m, 4H), 7.12 (dd, J = 7.7, 1.3 Hz, 2H), 7.16 (dt, J = 7.7,
1.3 Hz, 1H), 7.23 (t, J = 7.7 Hz, 2H), 7.28 (t, J = 7.9 Hz, 1H), 7.62
I
J. Org. Chem. XXXX, XXX, XXX−XXX