10.1002/adsc.201900177
Advanced Synthesis & Catalysis
From aldehyde 2b (50 mg, 0.30 mmol), by reaction with
OYE1 and EVO200, alcohol 10b (37.3 mg, 74%,
colourless oil) was obtained: []D = –3.3 (c 1.0, CHCl3);
1H NMR (400 MHz, CDCl3) δ 3.55 – 3.45 (m, 2H,
CH2OH), 2.15 – 2.11 (m, 2H, CH2C≡C), 2.11 – 2.03 (m,
2H, CH2C≡C), 1.84 – 1.72 (m, 1H, CHCH3), 1.49 –
1.36 (m, 2H, CH2), 1.34 – 1.20 (m, 4H, 2CH2), 0.91 (d,
the presence of Pd/C to afford (S)-(–)-13 (23.2 mg,
90%): []D = – 6.5 (c 0.8, CHCl3) [lit. ref. [32] []D = +
8.2, c 0.5, CHCl3) for (R)-13 with ee = 83%]; GC-MS
(EI) tr = 4.4 min, m/z 128 (M+, 2), 84 (100), 69 (50), 56
(57).
J
= 6.8 Hz, 3H, CHCH3), 0.83 (t, J = 7.0 Hz, 3H,
CH3CH2); 13C NMR (101 MHz, CDCl3) δ 82.1, 78.1,
67.5, 35.5, 31.2, 28.9, 22.9, 22.3, 18.8, 16.4, 14.1; GC-
MS (EI) tr = 14.7 min, m/z 168 (M+, 1), 111 (89), 97
(92), 79 (100). Compound (–)-10b (25.0 mg, 0.15
mmol) was hydrogenated with molecular H2 in the
presence of Pd/C to afford (S)-(–)-15 (22.7 mg, 88%):
[]D = –7.9 (c 0.8, CHCl3) [lit. ref. [20] []D = +8.7, c
2.5, CHCl3) for (R)-15]; 1H NMR (400 MHz, CDCl3)[31]
δ 3.51 (dd, J = 10.5, 5.8 Hz, 1H, CHHOH), 3.41 (dd, J =
10.5, 6.5 Hz, 1H, CHHOH), 1.65 – 1.55 (1H, m,
CHCH3), 1.45 – 1.20 (m, 14H, 7CH2), 0.95 – 0.80 (d+t,
J = 6.7 and 7.0 Hz, 6H, 2CH3); 13C NMR (101 MHz,
(R)-3-Methylhept-4-yn-1-ol ((R)-11b)
From aldehyde (Z)-3b (50 mg, 0.41 mmol), by reaction
with OYE3 and EVO200, alcohol 11b (40.3 mg, 78%,
colourless oil) was obtained (ee = 70%): H NMR (400
1
MHz, CDCl3) δ 3.86 – 3.73 (m, 2H, CH2OH), 2.63 –
2.53 (m, 1H, CHCH3), 2.21 – 2.12 (m, 2H, CH2C≡C),
1.75 – 1.60 (m, 2H, CH2CH2OH), 1.17 (d, J = 6.9 Hz,
3H, CHCH3), 1.11 (t, J = 7.5 Hz, 3H, CH3CH2); 13C
NMR (101 MHz, CDCl3) δ; 83.4, 82.8, 61.4, 39.8, 23.0,
21.7, 14.3, 12.4; GC-MS (EI) tr = 7.3 min, m/z 125 (M+-
CDCl3)[31] δ 68.6, 35.9, 33.3, 32.0, 30.1, 29.8, 29.5, 27.1, 1, 2), 111 (54), 97 (100), 79 (82).
22.8, 16.7, 14.2; GC-MS (EI) tr = 14.8 min, m/z 154
(M+–18, 2), 111 (20), 85 (45), 57 (100).
Acknowledgements
(R)-3-Methyl-5-phenylpent-4-ynal ((R)-8a)
Regione Lombardia (VIPCAT project no. 228775) is
From aldehyde (Z)-3a (50 mg, 0.29 mmol), by reaction
with OYE3, aldehyde (R)-8a (37.4 mg, 75%, pale
yellow oil) was obtained (ee = 87%, determined by
HPLC analysis of the corresponding saturated alcohol
12): []D = –24.0 (c 0.8, CH2Cl2) [lit. ref. [16d] []D = –
acknowledged for financial support.
References
1
24.8, c 0.5, CH2Cl2) for (R)-8a ee = 87%)]; H NMR
(400 MHz, CDCl3)[16d] δ 9.86 (t, J = 2.0 Hz, 1H, CHO),
7.44 – 7.34 (m, 2H, aromatic hydrogens), 7.33 – 7.21
(m, 3H, aromatic hydrogens), 3.21 (m, 1H, CHCH3),
2.69 (ddd, J = 16.7, 7.2, 2.0 Hz, CHH), 2.60 (1H, ddd, J
= 16.7, 6.6, 2.0 Hz, CHH), 1.34 (d, J = 6.9 Hz, 3H,
CHCH3); 13C NMR (101 MHz, CDCl3)[16d] δ 201.1,
131.7, 128.4, 128.0, 123.4, 92.2, 81.9, 50.2, 21.4, 21.2;
GC-MS (EI) tr = 17.2 min, m/z 172 (M+, 8), 157 (18),
129 (100), 115 (23), 102 (41). An analytical sample of
8a was treated first with NaBH4, then hydrogenated
with molecular H2 in the presence of Pd/C to afford
saturated alcohol 12, that was submitted to HPLC
analysis for ee determination: tR (R)-12 = 16.2 min, tR
(S)-12= 18.6 min.[17] The same procedure was repeated
on the other samples of 8a prepared by OYE-mediated
reduction of (E)- and (Z)-3a.
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[3] a) R. W. Powell, M. P. Buteler, S. Lenka, M. Crotti,
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8, 5003-5016; b) E. Brenna, M. Crotti, F. G. Gatti, D.
From aldehyde (Z)-3a (50 mg, 0.29 mmol), by reaction
with OYE3 and EVO200, alcohol (R)-11a (35.8 mg,
71%, pale yellow oil) was obtained (ee = 87%): []D = –
27.7 (c 0.8, CH2Cl2) [lit. ref. 16d] []D = –28.2, c 0.5,
CDCl3)[16d] δ 7.45 – 7.35 (m, 2H, aromatic hydrogens),
7.33 – 7.23 (m, 3H, aromatic hydrogens), 3.94 – 3.81
(m, 2H, CH2OH), 2.91 – 2.80 (m, 1H, CHCH3), 1.88 –
1.70 (m, 2H, CH2), 1.30 (d, J = 6.9 Hz, 3H, CHCH3);
13C NMR (101 MHz, CDCl3)[16d] δ 131.7, 128.4, 127.8,
123.8, 93.8, 81.6, 61.4, 39.8, 23.6, 21.4; GC-MS (EI) tr
= 18.8 min, m/z 174 (M+, 21), 159 (43), 141 (35), 128
(100).
1
CH2Cl2) for (R)-11a ee = 87%)]; H NMR (400 MHz,
Monti,
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Parmeggiani,
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Santangelo,
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(R)-3-Methylhept-4-yn-1-al ((R)-8b)
From aldehyde (Z)-3b (50 mg, 0.41 mmol), by reaction
with OYE3, aldehyde (R)-8b (40.1 mg, 79%, colourless
1
oil) was obtained (ee = 70%): H NMR (400 MHz,
CDCl3) δ 9.79 (t, J = 2.1 Hz, 1H, CHO), 3.00 – 2.88 (m,
1H, CHCH3), 2.59 – 2.41 (m, 2H, CH2CHO), 2.11 –
2.19 (m, 2H, CH2C≡C), 1.22 (d, J = 6.9 Hz, 3H,
CHCH3), 1.10 (t, J = 7.4 Hz, 3H, CH3); 13C NMR (101
MHz, CDCl3) δ 201.5, 83.0, 81.6, 50.1, 21.2, 20.6, 14.0,
12.1; GC-MS (EI) tr = 5.8 min, m/z 123 (M+–1, 3), 109
(100), 95 (27), 81 (66). A sample of this aldehyde (25.0
mg, 0.20 mmol) was hydrogenated with molecular H2 in
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B. Hauer, ChemBioChem 2012, 13, 2400-2407; b) E.
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9
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