天然产物1,3-二-(2-羟基-4-甲氧基苯基)丙烷和1,3-二-(2,4-二羟基苯基)丙烷的合成

1,3-二-(2-羟基-4-甲氧基苯基)丙烷(1)和1,3-二-(2,4-二羟基苯基)丙烷(2)是从菊叶薯蓣(Dioscorea composita Hemsl.)分离出来的天然产物, 以间苯二酚为起始原料, 分别经甲酰化和乙酰化得到2,4-二羟基苯甲醛和2,4-二羟基苯乙酮, 然后经选择性地甲基化、甲氧甲基化、羟醛缩合、还原、脱保护等步骤完成了上述两种天然产物的首次全合成. 产物通过¹H NMR, IR, MS进行了结构确证.

Syntheses of 1,3-Bis(2-hydroxy-4-methoxyphenyl)propane and 1,3-Bis(2,4-dihydroxyphenyl)propane

Two natural products 1,3-bis(2-hydroxy-4-methoxyphenyl)propane (1) and 1,3-bis(2,4-dihydr- oxyphenyl)propane (2), isolated from the dried rhizomes of Dioscorea composita Hemsl., were first synthesized by acylation, methoxymethyl protection or methylation, condensation, catalytic hydrogenation, deoxygenation and deprotection starting from resorcinol. 2,4-Dihydroxybenzaldehyde and 2,4-dihydroxyacetophenone were synthesized from resorcinol, which were followed by protection with standard methylation or methoxymethylation to afford 4-methoxy-2-methoxymethoxybenzaldehyde and 2-hydroxy-4-methoxyl- acetophenone. The desired chal-cone was obtained by condensing 4-methoxy- 2-methoxymethoxyben- zaldehyde with 2-hydroxy-4-methoxylacetophenone, which was then reducted by catalytic hydrogenation and deoxygena-tion to give the title compound 1,3-bis(2-hydroxy- 4-methoxyphenyl)propane (1). Another desired product 1,3-bis(2,4-dihydroxyphenyl)propane (2) was obtained by treatment of 1 with boron tribromide in anhydrous methylene dichloride. Their structures were confirmed by ¹H NMR, IR and MS techniques.