Andreas Farwick et al.
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6.8 Hz, 1H), 6.56 (d, J=15.8 Hz, 1H), 7.22–7.36 (m, 7H),
7.76–7.79 (m, 2H); 13C NMR (CDCl3, 75 MHz): d=3.4, 21.6,
36.6, 48.7, 71.9, 81.8, 123.5, 126.6, 128.0, 128.1, 128.7, 129.4,
134.6, 136.4, 136.4, 143.4; HR-MS (ESI+): m/z=340.1367
[M+H]+, calcd. for C20H22NO2S: 340.1366; elem. anal.
calcd. for C20H21NO2S: C 70.77, H 6.24, N 4.13, S 9.45;
found: C 70.64, H 6.18, N 4.25, S 9.64.
0.17 (s, 9H), 2.59 (d, J=17.2 Hz, 1H), 2.79 (d, J=17.2 Hz,
1H), 3.70 (s, 3H), 3.75 (s, 3H), 4.27 (d, J=8.1 Hz, 1H), 5.07
(ddd, J=17.0 Hz, J=1.5 Hz, J=1.5 Hz, 1H), 5.14 (ddd, J=
10.3 Hz, J=1.3 Hz, J=1.3 Hz, 1H), 6.43 (ddd, J=17.0 Hz,
J=10.3 Hz, J=8.1 Hz, 1H), 7.18–7.41 (m, 5H); 13C NMR
(CDCl3, 75 MHz): d=0.1, 25.9, 52.5, 52.6, 52.7, 61.7, 88.9,
101.9, 117.6, 127.4, 128.3, 129.5, 137.3, 138.8, 169.8, 169.9;
HR-MS (ESI+): m/z=359.1676 [M+H]+, calcd. for
C20H27O4Si: 359.1673.
Analytical data for dimethyl [(2E)-3-phenylprop-2-en-1-
yl][3-(trimethylsilyl)prop-2-yn-1-yl]malonate (3i): Colorless
oil. 1H NMR (CDCl3, 300 MHz): d=0.11 (s, 9H), 2.81 (s,
2H), 2.90 (dd, J=7.7 Hz, J=0.9 Hz, 2H), 3.69 (s, 6H), 5.96
(dt, J=15.5 Hz, J=7.6 Hz, 1H), 6.45 (d, J=15.7 Hz, 1H),
7.13–7.29 (m, 5H); 13C NMR (CDCl3, 75 MHz): d=0.1, 24.5,
36.1, 52.9, 57.6, 88.6, 101.4, 123.4, 126.4, 127.6, 128.6, 134.7,
137.2, 170.3; HR-MS (ESI+): m/z=359.1676 [M+H]+,
calcd. for C20H27O4Si: 359.1673.
Dimethyl But-2-yn-1-yl[(1S)-1-phenylprop-2-en-1-yl]-
malonate (2h) (Table 1, entry 9)
GP1 was carried out with [IrACHTNUTRGNENG(U COD)Cl]2 (13.8 mg, 20 mmol),
(S,S,aS)-L2 (24.9 mg, 40 mmol), TBD (13.1 mg, 95 mmol), cin-
namyl methyl carbonate (1a) (200 mg, 1.04 mmol), dimethyl
but-2-yn-1-ylmalonate (Nu6) (220 mg, 1.20 mmol) and dry
THF (1 mL); reaction time: 5 h at room temperature; TLC
monitoring [petroleum ether/ethyl acetate 4:1, Rf(1a)=0.36,
Rf(2h)=0.32, KMnO4]; ratio 2h:3h=93:07 (1H NMR).
Column chromatography on silica gel (petroleum ether/
ethyl acetate 95:5) afforded 2h as a yellowish oil; yield:
226 mg (0.75 mmol, 72%); [a]2D0: +13.0 (c 1.07, CHCl3);
HPLC (Daicel Chiralcel OD-H 4.6ꢅ250 mm with precol-
umn OD-H 10ꢅ4 mm, n-hexane/i-PrOH 99:01, flow=
0.5 mL/min, l=220 nm): tR[(+)-(S)-2h]=15.0 min, tR[(ꢀ)-
(R)-2h]=19.2 min; 1H NMR (CDCl3, 500 MHz): d=1.79
(dd, J=2.5 Hz, J=2.5 Hz, 3H), 2.49 (dq, J=16.9 Hz, J=
2.5 Hz, 1H), 2.69 (dq, J=16.8 Hz, J=2.5 Hz, 1H), 3.70 (s,
3H), 3.74 (s, 3H), 4.25 (d, J=8.1 Hz, 1H), 5.07 (ddd, J=
16.8 Hz, J=1.2 Hz, J=1.2 Hz, 1H), 5.14 (ddd, J=10.2 Hz,
J=0.8 Hz, J=0.8 Hz, 1H), 6.42 (ddd, J=17.0 Hz, J=
10.3 Hz, J=8.1 Hz, 1H), 7.18–7.29 (m, 5H); 13C NMR
(CDCl3, 125 MHz): d=3.7, 25.0, 52.4, 52.6, 52.6, 61.7, 73.9,
79.5, 117.4, 127.4, 128.3, 129.4, 137.6, 139.0, 170.0, 170.2;
HR-MS (ESI+): m/z=301.1434 [M+H]+, calcd. for
C18H21O4: 301.1434.
tert-Butyl {(1S)-1-[(1,1-Dimethylpropoxy)methyl]-
prop-2-en-1-yl}formylcarbamate (2j) (Table 1,
entry 11)
GP1 was carried out with [IrACHTNURGTNEUNG(COD)Cl]2 (202 mg,
0.30 mmol), (S,S,aS)-L2 (360 mg, 0.60 mmol), TBD (167 mg,
1.20 mmol), carbonate 1c (3.24 g, 15.0 mmol), tert-butyl for-
mylcarbamate (Nu8) (2.61 g, 18.0 mmol) and dry THF
(15 mL); reaction time: 1.5 h at 408C; TLC monitoring [pe-
troleum ether/ethyl acetate 9:1, Rf(1c)=0.42, Rf(2j)=0.52,
KMnO4]; ratio 2j:3j=81:19 (1H NMR). Column chromatog-
raphy on silica gel (petroleum ether/ethyl acetate 20:1!9:1)
afforded 2j as a colorless oil; yield: 2.66 g (9.32 mmol,
62%); [a]2D0: +10.9 (c 0.83, CHCl3); HPLC (Daicel Chiral-
pak AD-H 4.6ꢅ250 mm with precolumn AD-H 10ꢅ4 mm,
n-hexane/i-PrOH 99.5:0.5, flow=0.5 mL/min, l=220 nm):
1
Analytical data for dimethyl but-2-yn-1-ylACTHNUGRTENUNG[(2E)-3-phenyl-
tR[(ꢀ)-(R)-2j]=12.7 min, tR[(+)-(S)-2j]=13.7 min; H NMR
prop-2-en-1-yl]malonate (3h): Yellowish oil. 1H NMR
(CDCl3, 300 MHz): d=1.78 (dd, J=2.5 Hz, J=2.5 Hz, 3H),
2.79 (q, J=2.5 Hz, 2H), 2.94 (dd, J=7.6 Hz, J=1.1 Hz, 2H),
3.74 (s, 6H), 6.02 (dt, J=15.5 Hz, J=7.6 Hz, 1H), 6.49 (d,
J=15.7 Hz, 1H), 7.18–7.34 (m, 5H); 13C NMR (CDCl3,
75 MHz): d=3.6, 23.4, 36.1, 52.8, 57.7, 73.4, 79.2, 123.6,
126.4, 127.5, 128.6, 134.4, 137.2, 170.6; HR-MS (ESI+):
m/z=301.1435 [M+H]+, calcd. for C18H21O4: 301.1434.
(CDCl3, 400 MHz): d=0.81 (t, J=7.5 Hz, 3H), 1.07, 1.08
(2 s, 6H), 1.43 (dq, J=7.4 Hz, J=2.3 Hz, 2H), 1.53 (s, 9H),
3.50 (dd, J=9.0 Hz, J=6.1 Hz, 1H), 3.74 (dd, J=9.0 Hz, J=
9.0 Hz, 1H), 5.02–5.08 (m, 1H), 5.17 (ddd, J=10.5 Hz, J=
1.3 Hz, J=1.3 Hz, 1H), 5.20 (ddd, J=17.4 Hz, J=1.3 Hz,
J=1.3 Hz, 1H), 6.02 (ddd, J=17.2 Hz, J=10.4 Hz, J=
6.7 Hz, 1H), 9.21 (s, 1H); 13C NMR (CDCl3, 100 MHz): d=
8.3, 24.8, 25.1, 28.2, 33.3, 55.1, 61.1, 75.1, 84.0, 117.9, 134.1,
152.5, 163.5; HR-MS (ESI+): m/z=308.1833 [M+Na]+,
calcd. for C15H27NO4Na: 308.1832.
Dimethyl [(1S)-1-Phenylprop-2-en-1-yl][3-(trimethyl-
silyl)prop-2-yn-1-yl]malonate (2i) (Table 1, entry 10)
Analytical data for tert-butyl [(2E)-4-(1,1-dimethylpro-
poxy)but-2-en-1-yl]formylcarbamate (3j): Colorless oil.
1H NMR (CDCl3, 400 MHz): d=0.84 (t, J=7.5 Hz, 3H),
1.12 (s, 6H), 1.48 (q, J=7.5 Hz, 2H), 1.52 (s, 9H), 3.82 (dd,
J=5.2 Hz, J=1.1 Hz, 2H), 4.15 (dd, J=6.0 Hz, J=1.0 Hz,
2H), 5.64 (dtt, J=15.3 Hz, J=6.0 Hz, J=1.4 Hz, 1H), 5.71–
5.77 (m, 1H), 9.15 (s, 1H); 13C NMR (CDCl3, 100 MHz):
d=8.4, 25.2, 28.2, 32.7, 41.9, 61.4, 75.3, 84.1, 125.1, 132.2,
152.5, 162.8; HR-MS (ESI+): m/z=308.1835 [M+Na]+,
calcd. for C15H27NO4Na: 308.1832.
GP1 was carried out with [IrACHTNUTRGNENG(U COD)Cl]2 (13.7 mg, 20 mmol),
(S,S,aS)-L2 (24.5 mg, 40 mmol), TBD (13.1 mg, 95 mmol), cin-
namyl methyl carbonate (1a) (202 mg, 1.05 mmol), dimethyl
[3-(trimethylsilyl)prop-2-yn-1-yl]malonate (Nu7) (306 mg,
1.26 mmol) and dry THF (1 mL); reaction time: 3 h at room
temperature; TLC monitoring [petroleum ether/diethyl
ether 9:1, Rf(1a)=0.38, Rf(2i)=0.35, KMnO4]; ratio 2i:3i=
95:05 (1H NMR). Column chromatography on silica gel (pe-
troleum ether/ethyl acetate 95:5) afforded 2i as a colorless
oil; yield: 261 mg (0.73 mmol, 69%); [a]2D0: +5.7 (c 1.14,
CHCl3); HPLC (Daicel Chiralpak AD-H 4.6ꢅ250 mm with
precolumn AD-H 10ꢅ4 mm, n-hexane/i-PrOH 99.5:0.5,
flow=0.5 mL/min, l=220 nm): tR[(+)-(S)-2i]=13.3 min,
tR[(ꢀ)-(R)-2i]=16.5 min; 1H NMR (CDCl3, 300 MHz): d=
tert-Butyl {(1S)-1-[(1,1-Dimethylpropoxy)methyl]-
prop-2-en-1-yl}carbamate (2q)
KOH (203 mg, 3.62 mmol) was added to a solution of carba-
mate 2j (2.58 g, 9.04 mmol) in MeOH (45 mL). The mixture
358
ꢃ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2011, 353, 349 – 370