110(P42) 抗HIV-1活性Calophyllumクマリン合成へのアプローチ(ポスター発表の部)
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Some coumarins 1 isolated from Calophyllum genus (Guttiferae) (Fig. 1) showed strong anti HIV-1 activities, for which the stereochemistries of a 2,3-dimethyl-4-chromanol ring (A-D) in 1 should be most responsible. We examined the stereoselective preparation of a trans, trans chromanol ring. In our synthetic strategy a key reaction is an intramolecular Michael addition (IMA) of an o-tigloylphenol for the construction of a chromanone ring, which would be easily accessible to the desired chromanol ring through a Luche reduction. The starting phenols (3, 4) for IMA were prepared as shown in Scheme 1. After several trials for IMA of 3 under various conditions (Table 1), a high diastereoselectivity (90% de) was observed in the cyclization to a trans chromanone ring when 3 was treated with CsF (runs 5, 6) (the CsF-induced IMA). Furthermore, the cis chromanone (c-5) was found to be exclusively isomerized into the trans chromanone (t-5) under the same condition of the CsF-induced IMA (the CsF-mediated isomerization). The contribution of CsF to these strictly stereocontrolled reactions is reasonably speculated as shown in Scheme 2. Hydride reductions of the trans chromanone (t-5) were examined under various conditions. (Table 2) Although the reductions using boron hydride complexes, even if under the condition of Luch reduction (run 1), failed to the stereoselective production of the trans, trans chromanol (t, t-2) (runs 2-6), the use of aluminum hydride complexes (runs 7-9), especially a bulky lithium tri(t-butyl) aluminum hydride (LTBAH) (run 9), led to successful results. Application of the LTBAH reduction to the cis chromanone (c-5) quantitatively gave the cis, cis chromanol (c, c-2) as a sole reduction product. (Scheme 3) Next we tried IMA of 3 in the presence of chiral amines. (Table 3) Satisfactory enantioselectivity was observed in the cyclization to cis chromanone (c-5), when quinine (runs 1,2) or quinidine (run 3) was used.
- 天然有機化合物討論会の論文
- 1998-08-31
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