Esaki S, Nishiyama K, Sugiyama N, Nakajima R, Takao Y, Kamiya S
Department of Food Science, School of Food and Nutritional Sciences, University of Shizuoka, Japan.
Biosci Biotechnol Biochem. 1994 Aug;58(8):1479-85. doi: 10.1271/bbb.58.1479.
The 7-O-[2-O-(alpha-L-Rhamnopyranosyl)-beta-L-quinovoside] of naringenin and of hesperetin, and their dihydrochalcone (DHC) derivatives were synthesized by the method of Koenigs-Knorr (Ag2CO3 and quinoline). The reaction of TMS ethers of naringenin and of hesperetin with each of the alpha-acetofluoro derivatives of D-glucose, L-rhamnose, 2-O-(alpha-L-rhamnopyranosyl)-L-rhamnose, and 2-O-(alpha-L-rhamnopyranosyl)-D-glucose (neohesperidose), using boron trifluoride etherate as an activator, yielded coupling products which, after deprotection, gave naringenin 4'-O-beta-D-glucoside, naringenin 4'-O-alpha-L-rhamnoside, naringenin 4'-O-[2-O-(alpha-L-rhamnopyranosyl)-alpha-L-rhamnoside], hesperetin 3'-O-[2-O-(alpha-L-rhamnopyranosyl)-alpha-L-rhamnoside], and naringenin 4'-O-beta-neohesperidoside, respectively. Catalytic hydrogenation of these flavanones gave the corresponding DHC derivatives. Hesperetin DHC 4'-O-[2-O-(alpha-L-rhamnopyranosyl-beta-L-quinovoside] was 300 times sweeter than sucrose, while the other compounds were bitter or tasteless.
采用柯尼希斯－克诺尔法（碳酸银和喹啉）合成了柚皮素和橙皮素的7 - O - [2 - O -（α - L - 鼠李吡喃糖基）-β - L - 奎诺糖苷]及其二氢查耳酮（DHC）衍生物。以三氟化硼乙醚为活化剂，使柚皮素和橙皮素的TMS醚与D - 葡萄糖、L - 鼠李糖、2 - O -（α - L - 鼠李吡喃糖基）-L - 鼠李糖和2 - O -（α - L - 鼠李吡喃糖基）-D - 葡萄糖（新橙皮糖）的α - 乙酰氟衍生物分别反应，得到偶联产物，脱保护后分别得到柚皮素4'-O -β - D - 葡萄糖苷、柚皮素4'-O -α - L - 鼠李糖苷、柚皮素4'-O - [2 - O -（α - L - 鼠李吡喃糖基）-α - L - 鼠李糖苷]、橙皮素3'-O - [2 - O -（α - L - 鼠李吡喃糖基）-α - L - 鼠李糖苷]和柚皮素4'-O -β - 新橙皮糖苷。这些黄烷酮经催化氢化得到相应的DHC衍生物。橙皮素DHC 4'-O - [2 - O -（α - L - 鼠李吡喃糖基-β - L - 奎诺糖苷]的甜度是蔗糖的300倍，而其他化合物则有苦味或无味。
