Liu Zilei, Yoshihara Akihide, Kelly Ciarán, Heap John T, Marqvorsen Mikkel H S, Jenkinson Sarah F, Wormald Mark R, Otero José M, Estévez Amalia, Kato Atsushi, Fleet George W J, Estévez Ramón J, Izumori Ken
Chemistry Research Laboratory, Department of Chemistry, University of Oxford, Oxford, OX1 3TA, UK.
Glycobiology Institute, Department of Biochemistry, University of Oxford, Oxford, OX1 3QU, UK.
Chemistry. 2016 Aug 22;22(35):12557-65. doi: 10.1002/chem.201602482. Epub 2016 Jul 21.
In the search for alternative non-metabolizable inducers in the l-rhamnose promoter system, the synthesis of fifteen 6-deoxyhexoses from l-rhamnose demonstrates the value of synergy between biotechnology and chemistry. The readily available 2,3-acetonide of rhamnonolactone allows inversion of configuration at C4 and/or C5 of rhamnose to give 6-deoxy-d-allose, 6-deoxy-d-gulose and 6-deoxy-l-talose. Highly crystalline 3,5-benzylidene rhamnonolactone gives easy access to l-quinovose (6-deoxy-l-glucose), l-olivose and rhamnose analogue with C2 azido, amino and acetamido substituents. Electrophilic fluorination of rhamnal gives a mixture of 2-deoxy-2-fluoro-l-rhamnose and 2-deoxy-2-fluoro-l-quinovose. Biotechnology provides access to 6-deoxy-l-altrose and 1-deoxy-l-fructose.
在寻找鼠李糖启动子系统中可替代的非代谢性诱导剂时，由L-鼠李糖合成15种6-脱氧己糖证明了生物技术与化学协同作用的价值。鼠李糖内酯易于获得的2,3-丙酮化物可使鼠李糖C4和/或C5的构型发生反转，从而得到6-脱氧-D-阿洛糖、6-脱氧-D-古洛糖和6-脱氧-L-塔罗糖。高度结晶的3,5-亚苄基鼠李糖内酯可轻松制得L-奎诺糖（6-脱氧-L-葡萄糖）、L-橄榄糖以及带有C2叠氮基、氨基和乙酰氨基取代基 的鼠李糖类似物。鼠李醛的亲电氟化反应可得到2-脱氧-2-氟-L-鼠李糖和2-脱氧-2-氟-L-奎诺糖的混合物。生物技术可用于制备6-脱氧-L-阿卓糖和1-脱氧-L-果糖。
