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有机硼化合物是极其重要的有机合成中间体[1],特别是随着1971年诺贝尔化学奖得者H,CBrown成功地合成了第一个手性硼试剂,更使有机硼试剂进入不对称合成的新天地。1单取代硼酸的合成单取代硼酸通常可用硼酸与格氏试剂反应来制备[2]:众所周知,格氏反应需低温、无水、无氧。反应条件苛刻。我们在超声波的作用下,通过卤代烃、镁粉与硼酸正丁酯一锅反应成功地合成了单取代硼酸酯:反应条件温和,不必严格无水无氧,反应在室温下进行,产率在42%-60%之间。2 手性硼酸酯的合成手性硼酸酯是近年来发展起来的不对称合成试剂。目前合成手性硼酸酯应用最为成功的手性配体是α-蒎二醇[3]。我们利用我国丰产的高光学纯的雪松烯为原料,用四氧化锇催化氧化三甲胺氧化合成了与α-蒎二醇结构相似的a-雪松二醇:通过手性的雪松二醇和上述制备的单取代硼酸酯酯化,成功地合成了五个手性硼酸酯:本工作开创了一种新型的制备单取代硼酸的方法,合成了十一个化合物,其中六个系首次报道,并经IR,NMR,MS表征。
Organic boron compounds are very important organic synthesis intermediates [1], especially with the 1971 Nobel laureate H, CBrown successfully synthesized the first chiral boron reagent, but also make the organic boron reagent into the asymmetry Synthesis of the new world. 1 Monobasic boronic acid synthesis Monobasic boronic acid can usually boric acid and Grignard reagents to prepare [2]: It is well-known that the Grignard reaction to be low temperature, anhydrous, no oxygen. Harsh conditions. We under the action of ultrasound, halogenated hydrocarbons, magnesium powder and n-butyl borate one-pot reaction successfully synthesized monobasic boronate ester: mild reaction conditions, without strict anhydrous anaerobic, the reaction was carried out at room temperature, Rate between 42% -60%. 2 Chiral boronic ester synthesis Chiral boronic ester is developed in recent years asymmetric synthesis reagents. At present, the most successful chiral ligand for the synthesis of chiral boronic esters is α-pinanediol [3]. We use our high yield of pure optically pure cedrene as raw material, the catalytic oxidation of trimethylamine with osmium tetroxide to synthesize a-cedrol diol with similar structure to α-pinane diol: by the chiral cedrol and the above prepared Five boronic acid esters were successfully synthesized by esterification of monobasic boronic ester. This work pioneered a novel method for the preparation of monobasic boronic acid. Eleven compounds were synthesized, of which six were first reported and Characterized by IR, NMR, MS.