Abstract
(+)-Preussin was synthesized in ten steps with an overall yield of 6.4% from phenylacetaldehyde. The three stereogenic centers were controlled by enantioselective allyltitanations of aldehydes.
Key words
preussin - allyltitanation - cross-metathesis
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6 Complex (R ,R )-Ia (R = MOM) was formed in situ after deprotonation of 3-methoxymethoxypropene by s -BuLi and transmetallation with the correponding chlorocyclo-pentadienyldialkoxytitanium(IV) complex.
7 The enantiomeric excess of (+)-3 was determined by 1 H NMR after its derivatization with (S )- and (R )-methoxy-phenylacetic acid.
8 Secondary alcohol 4′ was isolated as a mixture of two diastereomers in a 75:25 ratio. After debenzylation (H2 , Pd/C, quantitative yield), the resulting 1,3-diols were transformed to the corresponding acetonides (dimethoxypropane, PPTS, 90%). According to the 1 H NMR and 13 C NMR data, the major product has the anti -anti structure (Figure
[3 ]
):
Figure 3
9 Decomposition of the starting material or non-reactivity were observed when other boranes were used [9-BBN, (Cy)2 BH].
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11 The formation of tetrahydrofuran B as secondary product could be observed during the cyclization process (Figure
[4 ]
).
Figure 4