CAJ | 학술논문

以D-核糖为原料,在微波促进下,利用2,3-O-异丙叉基-D-核糖2与叶立德3(Ph3P CHCOOEt)的Wittig反应和Michael加成,立体专一性地合成了β-D-呋喃核糖酸酯类化合物,再经叠氮化及还原反应,得到ω-氨基-β-D-呋喃核糖酸衍生物。在微波辐射下,该Wittig-Michael串级反应的效率得到显著提高,反应时间由12 h缩短为10 min,收率达到91%。反应具有非常好的β-立体选择性,在碱性条件下处理后,α-异构体可转变成热力学稳定的β-异构体,从而得到单一的β-异构体。计算结果表明,β-异构体4b比α-异构体4a具有更高的热力学稳定性。
이D-핵당위원료,재미파촉진하,이용2,3-O-이병차기-D-핵당2여협립덕3(Ph3P CHCOOEt)적Wittig반응화Michael가성,입체전일성지합성료β-D-부남핵당산지류화합물,재경첩담화급환원반응,득도ω-안기-β-D-부남핵당산연생물。재미파복사하,해Wittig-Michael천급반응적효솔득도현저제고,반응시간유12 h축단위10 min,수솔체도91%。반응구유비상호적β-입체선택성,재감성조건하처리후,α-이구체가전변성열역학은정적β-이구체,종이득도단일적β-이구체。계산결과표명,β-이구체4b비α-이구체4a구유경고적열역학은정성。
An efficient and stereoselective method for synthesizing ω-amino-β-D-furanoribosylactic ester was established based on the microwave assisted Wittig-Michael tandem reaction of acetone protection of D-ribose (2) and Ylide 3(Ph3P CHCOOEt), and followed by ω-azidation and reduction. The microwave assisted Wittig-Michael addition reaction was carried out effectively andβ-stereoselectively in CH3 CN at 115 ℃ with a yield up to 91% within 10 min, and theα-stereomer could easily converted to the thermodynamically more sta-ble β-stereomer during workup in basic condition. The calculation results of quantum chemistry show thatβ-isomer 4b is higher thanα-isomer 4a in thermodynamic stability. The structures of the compounds were iden-tified by spectral analyses of 1 H NMR, 13 C NMR and HRMS.