N
K. J. Hock et al.
Paper
Synthesis
1H NMR (400 MHz, CDCl3): δ = 5.91 (ddt, J = 17.0, 10.5, 5.7 Hz, 1 H),
5.35–5.20 (m, 2 H), 4.57 (dt, J = 5.7, 1.3 Hz, 2 H), 4.47–4.38 (m, 1 H),
3.96 (dd, J = 32.0, 28.3 Hz, 1 H), 2.32 (t, J = 7.5 Hz, 2 H), 1.83–1.71 (m,
1 H), 1.68–1.56 (m, 2 H), 1.56–1.21 (m, 24 H), 0.88 (t, J = 6.8, 6.0 Hz, 3
H) (peaks are not assigned to individual stereoisomers).
13C NMR (101 MHz, CDCl3): δ = 173.65, 132.48, 118.21, 93.00, 92.50,
77.16, 72.54, 72.21, 65.07, 34.38, 33.78, 33.36, 31.78, 30.60, 29.31,
29.26, 29.24, 29.19, 29.17, 29.16, 29.11, 29.08, 29.03, 28.10, 26.08,
25.81, 25.73, 25.40, 25.03, 22.67, 14.16 (peaks are not assigned to in-
dividual stereoisomers).
1H NMR (400 MHz, CDCl3): δ = 5.91 (ddt, J = 16.2, 10.5, 5.7 Hz, 1 H),
5.35–5.20 (m, 2 H), 4.57 (dt, J = 5.7, 1.3 Hz, 2 H), 4.52–4.36 (m, 1 H),
4.05–3.80 (m, 1 H), 2.32 (t, J = 7.5 Hz, 2 H), 2.20–1.98 (m, 1 H), 1.81–
1.71 (m, 1 H), 1.60 (dd, J = 18.8, 14.7 Hz, 2 H), 1.55–1.21 (m, 19 H),
0.88 (dd, J = 6.8, 6.0 Hz, 3 H) (peaks are not assigned to individual ste-
reoisomers).
13C NMR (101 MHz, CDCl3): δ = 173.55, 173.53, 132.45, 118.26, 92.97,
92.46, 77.16, 72.53, 72.21, 65.10, 34.30, 33.77, 33.37, 31.77, 30.56,
29.15, 29.10, 29.02, 29.01, 28.97, 28.92, 28.87, 28.07, 26.03, 25.75,
25.72, 25.40, 24.93, 22.67, 14.15 (peaks are not assigned to individual
stereoisomers).
MS (ESI): m/z [M + Na]+ calcd for C21H39NO5Na: 408.3; found: 408.3.
MS (ESI): m/z [M + Na]+ calcd for C19H35NO5Na: 380.2; found: 380.3.
Allyl 10-Hydroxy-9-nitrododecanoate (11i)
Allyl 10-Hydroxy-9-nitrohexadecanoate (11l)
Prepared from allyl 9-nitrononanoate (2a; 1.0 equiv, 1.6 mmol, 389
mg), propanal (3i; 1.2 equiv, 2.0 mmol, 116 mg), and TMG (0.2 equiv,
0.3 mmol, 0.04 mL) according to GP 5. Purification by flash column
chromatography (n-hexane/EtOAc 50:1 → 20:1) afforded a mixture of
isomers as a yellow liquid (299 mg, 62%, d.r. 42:58); Rf = 0. 4 (n-hex-
ane/EtOAc 9:1).
1H NMR (400 MHz, CDCl3): δ = 5.97–5.84 (m, 2 H), 5.35–5.19 (m, 2 H),
4.57 (dt, J = 5.7, 1.3 Hz, 2 H), 4.50–4.39 (m, 1 H), 3.97–3.74 (m, 1 H),
2.32 (t, J = 7.3 Hz, 2 H), 2.14–1.97 (m, 1 H), 1.76 (ddd, J = 15.7, 9.6, 4.7
Hz, 1 H), 1.68–1.40 (m, 4 H), 1.30 (s, 8 H), 1.02 (td, J = 7.4, 4.2 Hz, 3 H)
(peaks are not assigned to individual stereoisomers).
Prepared from allyl 9-nitrononanoate (2a; 1.0 equiv, 1.6 mmol, 389
mg), undecanal (3l; 1.2 equiv, 2.0 mmol, 340 mg), and TMG (0.2 equiv,
0.3 mmol, 0.04 mL) according to GP 5. Purification by flash column
chromatography (n-hexane/EtOAc 50:1 → 20:1) afforded a mixture of
isomers as a yellow liquid (457 mg, 69%, d.r. 37:63); Rf = 0.4 (n-hex-
ane/EtOAc 9:1).
1H NMR (400 MHz, CDCl3): δ = 5.91 (ddt, J = 17.1, 10.5, 5.7 Hz, 1 H),
5.26 (ddq, J = 28.1, 10.4, 1.4 Hz, 2 H), 4.57 (dt, J = 5.7, 1.3 Hz, 2 H),
4.49–4.37 (m, 1 H), 3.92 (dtd, J = 11.3, 8.0, 5.2 Hz, 1 H), 2.39–2.27 (m,
2 H), 2.23–1.92 (m, 1 H), 1.75 (dt, J = 9.5, 5.4 Hz, 1 H), 1.60 (dd, J =
17.8, 10.7 Hz, 2 H), 1.55–1.18 (m, 26 H), 0.87 (t, J = 6.8 Hz, 3 H) (peaks
are not assigned to individual stereoisomers).
13C NMR (101 MHz, CDCl3): δ = 173.54, 173.52, 132.44, 118.25, 92.97,
92.46, 77.16, 72.52, 72.21, 65.10, 34.29, 33.76, 33.36, 32.01, 30.56,
29.69, 29.66, 29.58, 29.49, 29.43, 29.00, 28.97, 28.92, 28.87, 28.08,
26.03, 25.75, 25.43, 24.92, 22.80, 14.23 (peaks are not assigned to in-
dividual stereoisomers).
13C NMR (101 MHz, CDCl3): δ = 173.54, 132.44, 118.25, 92.63, 92.16,
77.16, 73.86, 73.45, 65.10, 34.29, 30.53, 29.00, 28.99, 28.96, 28.91,
28.86, 28.12, 26.77, 26.45, 26.00, 25.73, 24.92, 10.15, 9.79 (peaks are
not assigned to individual stereoisomers).
MS (ESI): m/z [M + H]+ calcd for C15H28NO5: 302.2; found: 302.3.
Allyl 10-Hydroxy-9-nitrotetradecanoate (11j)
MS (ESI): m/z [M + Na]+ calcd for C23H44NO5Na: 414.3; found: 414.4.
Prepared from allyl 9-nitrononanoate (2a; 1.0 equiv, 1.6 mmol, 389
mg), pentanal (3j; 1.2 equiv, 2.0 mmol, 172 mg), and TMG (0.2 equiv,
0.3 mmol, 0.04 mL) according to GP 5. Purification by flash column
chromatography (n-hexane/EtOAc 50:1 → 20:1) afforded a mixture of
isomers as a yellow liquid (311 mg, 60%, d.r. 43:57); Rf = 0.4 (n-hex-
ane/EtOAc 9:1).
1H NMR (400 MHz, CDCl3): δ = 5.91 (ddt, J = 17.1, 10.5, 5.7 Hz, 1 H),
5.26 (dddd, J = 10.4, 3.6, 2.7, 1.3 Hz, 2 H), 4.57 (dt, J = 5.7, 1.3 Hz, 2 H),
4.48–4.36 (m, 1 H), 4.04–3.80 (m, 1 H), 2.33 (dd, J = 14.2, 6.7 Hz, 3 H),
1.76 (tt, J = 9.5, 4.6 Hz, 2 H), 1.62 (t, J = 7.0 Hz, 2 H), 1.54–1.41 (m, 2 H),
1.40–1.23 (m, 10 H), 0.91 (tt, J = 7.3, 3.8 Hz, 3 H) (peaks are not as-
signed to individual stereoisomers).
13C NMR (101 MHz, CDCl3): δ = 173.55, 173.53, 132.44, 118.26, 92.96,
92.46, 77.16, 72.51, 72.19, 65.10, 34.29, 33.45, 33.05, 30.56, 29.01,
29.00, 28.97, 28.92, 28.87, 28.07, 27.89, 27.56, 26.02, 25.75, 24.93,
22.58, 22.53, 14.04 (peaks are not assigned to individual stereoiso-
mers).
Allyl 10-Hydroxy-9-nitrodocosanoate (11m)
Prepared from allyl 9-nitrononanoate (2a; 1.0 equiv, 1.6 mmol, 389
mg), tridecanal (3m; 1.2 equiv, 2.0 mmol, 397 mg), and TMG (0.2
equiv, 0.3 mmol, 0.04 mL) according to GP 5. Purification by flash col-
umn chromatography (n-hexane/EtOAc 50:1 → 20:1) afforded a mix-
ture of isomers as a yellow liquid (494 mg, 70%, d.r. 40:60); Rf = 0.4 (n-
hexane/EtOAc 9:1).
1H NMR (400 MHz, CDCl3): δ = 5.91 (ddt, J = 17.1, 10.5, 5.7 Hz, 1 H),
5.26 (dddd, J = 28.2, 10.4, 2.8, 1.4 Hz, 2 H), 4.56 (dt, J = 5.7, 1.3 Hz, 2 H),
4.51–4.32 (m, 1 H), 4.04–3.72 (m, 1 H), 2.39–2.18 (m, 2 H), 2.16–1.94
(m, 1 H), 1.76 (tt, J = 9.4, 4.7 Hz, 1 H), 1.69–1.55 (m, 2 H), 1.54–1.17
(m, 30 H), 0.87 (t, J = 6.8 Hz, 3 H) (peaks are not assigned to individual
stereoisomers).
13C NMR (101 MHz, CDCl3): δ = 173.54, 173.52, 132.43, 118.24, 92.98,
92.46, 77.16, 72.52, 72.20, 65.09, 34.28, 33.74, 33.36, 32.03, 30.54,
29.77, 29.75, 29.73, 29.66, 29.59, 29.49, 29.46, 29.44, 29.01, 29.00,
28.97, 28.92, 28.86, 28.08, 26.02, 25.75, 25.42, 24.92, 22.80, 14.23
(peaks are not assigned to individual stereoisomers).
MS (ESI): m/z [M + H]+ calcd for C17H32NO5: 330.2; found: 330.2.
Allyl 10-Hydroxy-9-nitrohexadecanoate (11k)
MS (ESI): m/z [M + Na]+ calcd for C25H47NO5Na: 464.3; found: 464.4.
Prepared from allyl 9-nitrononanoate (2a; 1.0 equiv, 1.6 mmol, 389
mg), heptanal (3k; 1.2 equiv, 2.0 mmol, 288 mg), and TMG (0.2 equiv,
0.3 mmol, 0.04 mL) according to GP 5. Purification by flash column
chromatography (n-hexane/EtOAc 50:1 → 20:1) afforded a mixture of
isomers as a yellow liquid (326 mg, 57%, d.r. 50:50); Rf = 0.4 (n-hex-
ane/EtOAc 9:1).
Allyl 9-Hydroxy-10-nitrooctadecanoate (10a)
Prepared from allyl 7-oxononanoate (5a; 1.0 equiv, 3.3 mmol, 700
mg), 1-nitrononane (7a; 1.2 equiv, 4.1 mmol, 710 mg), and TMG (0.2
equiv, 0.7 mmol, 0.08 mL) according to GP 5. Purification by flash col-
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–V