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DOI: 10.1055/s-0031-1290658
A Short-Step Asymmetric Synthesis of Dehydrodiconiferyl Alcohol via C-H Insertion Reaction
Publikationsverlauf
Publikationsdatum:
28. März 2012 (online)
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Abstract
A rhodium-catalyzed intramolecular C-H insertion reaction using a chiral auxiliary and a chiral catalyst was employed to achieve double asymmetric induction of a trans-disubstituted dihydrobenzofuran ring, as the key reaction of a stereoselective synthesis of (-)-dehydrodiconiferyl alcohol in 13 steps from commercially available guaiacol.
Key words
neolignan - dehydrodiconiferyl alcohol - rhodium - C-H insertion - double asymmetric induction
- Supporting Information for this article is available online:
- Supporting Information
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References and Notes
This reaction was found to be sensitive to the reaction temperature: when the reaction was carried out at 0 ˚C, the chemical yield was decreased significantly due to the formation of an α-hydroxylated byproduct. Interestingly, reverse diastereoselectivity was observed at -20 ˚C, giving the product in 57% yield with a cis-substituted isomer being major (2.4:1 dr). Although the reason is unclear, these results suggest that careful control of the reaction temperature is necessary to ensure that the desired reaction pathway operates.
19As for the detailed discussion on the determination of the stereochemistry, see the Supporting Information.
21It seems likely that the observed absolute stereochemistry is mainly governed by the chiral auxiliary, and not by the chiral Rh catalyst, in accord with our previous results.¹²
24
Spectral Data
for 1
IR (neat): 818, 856, 966, 1034, 1146, 1215,
1275, 1331, 1464, 1496, 1518, 1603, 1703, 2361, 2926, 3414 cm-¹.
¹H
NMR (500 MHz, acetone-d
6): δ = 2.82
(s, 2 H), 3.52 (q, J = 6.3
Hz, 1 H), 3.81 (s, 3 H), 3.83-3.90 {m, 5 H [a
methoxy group (3 H) was included at δ = 3.85 ppm
as a singlet peak]}, 4.20 (dt, J = 1.2,
5.2 Hz, 2 H), 5.55 (d, J = 6.3
Hz, 1 H), 6.23 (td, J = 5.2,
16.0 Hz, 1 H), 6.51 (d, J = 16.0
Hz, 1 H), 6.80 (d, J = 8.0
Hz, 1 H), 6.87 (dd, J = 1.7,
8.0 Hz, 1 H), 6.94 (d, J = 1.2
Hz, 1 H), 6.97 (s, 1 H), 7.03 (d, J = 1.7
Hz, 1 H), 7.59 (s, 1 H). ¹³C NMR (125
MHz, acetone-d
6): δ = 54.0,
55.4, 55.5, 62.6, 63.8, 87.7, 109.6, 110.8, 114.8, 115.2, 118.8, 127.6,
129.6, 129.7, 131.1, 133.6, 144.4, 146.5, 147.5, 148.1. MS-FAB: m/z = 358 [M]+.
HRMS: m/z calcd for C20H22NaO6 [M + Na]+:
381.1314; found: 381.1309. [α]D
²³
-45.9
(c 2.67, acetone).