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54.2, 82.3, 115.0, 139.2, 153.0 ppm. HRMS (ESI+) calcd. for
C17H35N2O4 [M + Me3NH]+ 331.2597; found 331.2592.
Di-tert-butyl ((2E)-4-{[tert-Butyl(dimethyl)-silyl]oxy}but-2-en-1-
yl)imidodicarbonate (3f): H NMR (CDCl3, 400 MHz): δ = 0.06 (s, 6
1
H), 0.90 (s, 9 H), 1.49 (s, 18 H), 4.13–4.17 (m, 4 H), 5.65–5.77 (m, 2
H) ppm. 13C NMR (CDCl3, 100 MHz): δ = –5.1, 18.5, 26.1, 28.2, 47.6,
63.3, 82.4, 125.6, 132.2, 152.4 ppm. HRMS (ESI+) calcd. for
Di-tert-butyl (2E)-But-2-en-1-ylimidodicarbonate (3b): The ana-
lytical data were in agreement with the literature.[15]
(–)-Di-tert-butyl [(1R)-1-Hexylprop-2-en-1-yl]imidodicarbonate
(2c): This compound was prepared as described in General Proce-
dure 2; yield 471 mg (1.38 mmol), 69 %, colorless oil, 98 % ee (deter-
mined after mono-Boc removal), 2c/3c = 94:6. [α]D20 (95 % ee) = +2.6
[c = 1.00, CHCl3, (S)]. 1H NMR (CDCl3, 400 MHz): δ = 0.87 (t, J =
6.8 Hz, 3 H), 1.23–1.34 (m, 8 H), 1.48 (s, 18 H), 1.63–1.73 (m, 1 H),
1.79–1.90 (m, 1 H), 4.56–4.65 (m, 1 H), 5.09 (td, J = 10.3, 1.3 Hz, 1
H), 5.15 (td, J = 17.3, 1.4 Hz, 1 H), 6.00 (ddt, J = 17.2, 10.3, 6.7 Hz, 1
H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 14.2, 22.7, 26.5, 28.2, 29.1,
31.9, 32.6, 59.3, 82.2, 116.2, 138.2, 153.2 ppm. HRMS (ESI+) calcd. for
C
20H39NO5SiNa [M + Na]+ 424.2495; found 424.2489.
(–)-Di-tert-butyl [(1R)-1-(2-Phenylethyl)prop-2-en-1-yl]imidodi-
carbonate (2g): This compound was prepared as described in Gen-
eral Procedure 1; yield 384 mg (1.06 mmol), 78 %, colorless oil,
98 % ee (determined after mono-Boc removal), 2g/3g = 98:2. [α]D20
(98 % ee) = –0.4 [c = 1.03, CHCl3, (R)], ref.[16] [α]D20 (93 % ee) = –0.5
[c = 1.09, CHCl3, (S)]. The analytical data were in agreement with
the literature.
Di-tert-butyl
[(2E)-5-Phenylpent-2-en-1-yl]imidodicarbonate
C
19H35NO4Na [M + Na]+ 364.2464; found 364.2465.
1
(3g): H NMR (CDCl3, 300 MHz): δ = 1.49 (s, 18 H), 2.34 (dt, J = 7.3,
6.9 Hz, 1 H), 2.68 (t, J = 7.3 Hz, 2 H), 4.10 (dd, J = 5.9, 0.8 Hz, 1 H),
5.51 (dtt, J = 15.3, 6.0, 1.2 Hz, 1 H), 5.67 (dt, J = 15.4, 6.7 Hz, 1 H),
7.13–7.31 (m, 5 H) ppm. 13C NMR (CDCl3, 75 MHz): δ = 28.2, 34.2,
35.8, 48.0, 82.3, 126.0, 126.0, 128.4, 128.5, 132.8, 141.9, 152.6 ppm.
HRMS (ESI+) calcd. for C21H31NO4Na [M + Na]+ 384.2151; found
384.2148.
Di-tert-butyl (2E)-Non-2-en-1-ylimidodicarbonate (3c): 1H NMR
(CDCl3, 400 MHz): δ = 0.87 (t, J = 6.8 Hz, 3 H), 1.23–1.37 (m, 8 H),
1.49 (s, 18 H), 2.00 (q, J = 6.9, 6.8 Hz, 2 H), 4.09 (d, J = 6.0 Hz, 2 H),
5.40–5.50 (m, 1 H), 5.55–5.65 (m, 1 H) ppm. 13C NMR (CDCl3,
100 MHz): δ = 14.1, 22.6, 28.8, 29.2, 31.7, 28.1, 32.2, 48.0, 82.0, 125.1,
133.9, 152.4 ppm. HRMS (ESI+) calcd. for C19H35NO4Na [M + Na]+
364.2464; found 364.2464.
(–)-tert-Butyl [(1S)-1-Phenylprop-2-en-1-yl]carbamate (4a): This
compound was prepared as described in General Procedure 3; yield
551 mg (2.36 mmol), 96 %, colorless solid, m.p. 56–57 °C, ref.[14]
54–55 °C. [α]D20 (99 % ee) = –64.4 [c 1.00, CHCl3, (S)], ref.[14] [α]D20
(99 % ee) = +62.2 [c = 1.00, CHCl3, (R)]. The analytical data were in
(+)-Di-tert-butyl [(2S)-1-(Trityloxy)but-3-en-2-yl]imidodicarbon-
ate (2d): This compound was prepared as described in General
Procedure 2; yield 450 mg (0.85 mmol), 85 %, colorless solid, m.p.
140–143 °C, ref.[6d] 143–146 °C, 99 % ee (determined after mono-
Boc removal), 2d/3d = 94:6. [α]D20 (99 % ee) = +24.5 [c = 1.12, CHCl3, agreement with the literature.
(S)], ref.[6d] [α]D20 (97 % ee) = +25.7 [c = 0.97, CHCl3, (S)]. The analytical
data were in agreement with the literature.
(–)-tert-Butyl [(1S)-1-Methylprop-2-en-1-yl]carbamate (4b): This
compound was prepared as described in General Procedure 3; yield
126 mg (0.74 mmol), 95 %; colorless solid, m.p. 56–57 °C.
[α]D20 (98 % ee) = –4.9 [c = 1.09, CHCl3, (S)], ref.[17] [α]D20 = –6.3 [c =
1.2, CHCl3, (S)]. The analytical data were in agreement with the liter-
ature.
Di-tert-butyl [(2E)-4-(Trityloxy)but-2-en-1-yl]imidodicarbonate
(3d): The analytical data were in agreement with the literature.[6d]
(–)-Di-tert-butyl
{(1R)-1-[(Benzyloxy)methyl]prop-2-en-1-yl}-
imidodicarbonate (2e): This compound was prepared as described
in General Procedure 1; yield 122 mg (0.32 mmol), 76 %, colorless
oil, 93 % ee (determined after mono-Boc removal), 2e/3e = 92:8. [α]
(–)-tert-Butyl [(1R)-1-Hexylprop-2-en-1-yl]carbamate (4c): This
compound was prepared as described in General Procedure 3; yield
80.5 mg (0.33 mmol), 97 %, colorless oil. [α]D20 (98 % ee) = –12.4 [c =
1.55, CHCl3, (R)]. HPLC (Chiralpak AS-H, n-hexane/2-propanol
99.5:0.5, flow 0.5 mL min–1, room temp., λ = 205 nm), tR[(–)-(R)-4c] =
12.8 min, tR[(+)-(S)-4c] = 16.9 min. 1H NMR (CDCl3, 400 MHz): δ =
0.87 (t, J = 6.9 Hz, 3 H), 1.20–1.36 (m, 8 H), 1.40–1.54 (m, 2 H), 1.44
(s, 9 H), 4.07 (br. s, 1 H), 4.44 (br. s, 1 H), 5.06 (td, J = 10.4, 1.3 Hz, 1
H), 5.13 (td, J = 17.2, 1.3 Hz, 1 H), 5.73 (ddd, J = 17.1, 10.4, 5.7 Hz,
1 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 14.2, 22.7, 25.8, 28.5, 29.2,
31.9, 35.4, 52.9, 79.3, 114.3, 139.3, 155.5 ppm. HRMS (ESI+) calcd. for
C14H27NO2Na [M + Na]+ 264.1939; found 264.1934.
20 (93 % ee) = –10.4 [c = 1.01, CHCl3, (R)]. 1H NMR (CDCl3, 400 MHz):
D
δ = 1.48 (s, 18 H), 3.70 (dd, J = 9.8, 6.4 Hz, 1 H), 3.88 (dd, J = 9.8,
8.2 Hz, 1 H), 4.52 (d, J = 12.0 Hz, 1 H), 4.56 (d, J = 12.0 Hz, 1 H),
4.96–5.05 (m, 1 H), 5.18 (td, J = 10.6, 1.2 Hz, 1 H), 5.25 (td, J = 17.4,
1.2 Hz, 1 H), 5.96 (ddd, J = 17.1, 10.5, 6.1 Hz, 1 H), 7.22–7.36 (m, 5
H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 28.2, 58.1, 70.7, 72.9, 82.4,
117.5, 127.6, 127.7, 128.4, 134.8, 138.5, 153.1 ppm. HRMS (ESI+)
calcd. for C21H31NO5Na [M + Na]+ 400.2100; found 400.2093.
Di-tert-butyl [(2E)-4-(Benzyloxy)but-2-en-1-yl]imidodicarbonate
1
(3e): H NMR (CDCl3, 400 MHz): δ = 1.50 (s, 18 H), 3.97–4.04 (m, 2
H), 4.15–4.22 (m, 2 H), 4.50 (s, 2 H), 5.66–5.84 (m, 2 H), 7.24–7.38
(m, 5 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 28.2, 47.6, 70.2, 72.0,
82.5, 127.7, 127.8, 128.5, 128.9, 129.2, 138.4, 152.5 ppm. HRMS (ESI+)
calcd. for C21H31NO5Na [M + Na]+ 400.2100; found 400.2093.
(–)-tert-Butyl (S)-[1-(Trityloxy)but-3-en-2-yl]carbamate (4d): A
solution of 2d (185 mg, 0.35 mmol) in a mixture of toluene (1 mL)
and EtOH (10 mL) was treated with KOH (39.2 mg, 0.51 mmol). Then
the mixture was stirred under reflux until TLC monitoring showed
complete conversion [petroleum ether/diethyl ether (10:1); Rf(2d) =
(–)-Di-tert-butyl [(1R)-1-({[tert-Butyl(dimethyl)silyl]oxy}methyl)-
prop-2-en-1-yl]imidodicarbonate (2f): This compound was pre- 0.38, Rf(4d) = 0.23, KMnO4]. The solvent was removed in vacuo, and
pared as described in General Procedure 1; yield 108 mg
the crude product was subjected to flash column chromatography
(0.27 mmol), 73 %, colorless oil, 89 % ee (determined after mono-
on silica gel [petroleum ether/diethyl ether (20:1)] to give 4d
Boc removal), 2f/3f = 93:7. [α]D20 (89 % ee) = –8.2 [c = 1.02, CHCl3, (133.8 mg, 0.31 mmol, 89 %) as a colorless oil. [α]D20 (99 % ee) =
1
(R)]. H NMR (CDCl3, 400 MHz): δ = 0.04 (s, 6 H), 0.88 (s, 9 H), 1.49
–18.5 [c = 1.05, CHCl3, (S)]. HPLC (Chiralpak AD-H, n-hexane/2-
(s, 18 H), 3.76 (dd, J = 9.9, 6.4 Hz, 1 H), 4.00 (dd, J = 9.9, 8.5 Hz, 1
propanol 95:5, flow 0.5 mL min–1, room temp., λ = 220 nm), tR[(+)-
H), 4.78–4.84 (m, 1 H), 5.16 (td, J = 10.5, 1.4 Hz, 1 H), 5.18 (td, J = (R)-4d] = 12.6 min, tR[(–)-(S)-4d] = 15.2 min. 1H NMR (CDCl3,
17.4, 1.4 Hz, 1 H), 5.92 (ddd, J = 17.4, 10.5, 6.2 Hz, 1 H) ppm. 13C 500 MHz): δ = 1.48 (s, 18 H), 3.20–3.26 (m, 2 H), 4.42 (br. s, 1 H),
NMR (CDCl3, 100 MHz): δ = –5.2, 18.4, 26.0, 28.2, 60.9, 63.9, 82.2, 4.87 (br. s, 1 H), 5.23 (td, J = 10.0, 1.5 Hz, 1 H), 5.29 (td, J = 17.3,
117.4, 134.7, 153.2 ppm. HRMS (ESI+) calcd. for C20H39NO5SiNa [M
+ Na]+ 424.2495; found 424.2488.
1.3 Hz, 1 H), 5.94 (ddd, J = 17.1, 10.5, 5.0 Hz, 1 H), 7.27–7.30 (m, 3
H), 7.34–7.37 (m, 6 H), 7.48–7.50 (m, 6 H) ppm. 13C NMR (CDCl3,
Eur. J. Org. Chem. 2016, 493–501
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