A NEW REAGENT FOR THE REMOVAL OF THE 4-METHOXYBENZYL ETHER - APPLICATION TO THE SYNTHESIS OF UNUSUAL MACROCYCLIC AND BOLAFORM PHOSPHATIDYLCHOLINES
A NEW REAGENT FOR THE REMOVAL OF THE 4-METHOXYBENZYL ETHER - APPLICATION TO THE SYNTHESIS OF UNUSUAL MACROCYCLIC AND BOLAFORM PHOSPHATIDYLCHOLINES
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DOI：
10.1021/jo00032a033
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发表时间：
1992-03-13
影响因子：
3.6
通讯作者：
JUST, G
中科院分区：
文献类型：
--
作者：
HEBERT, N;BECK, A;JUST, G
以3-（4-甲氧苄基）-sn-甘油10为起始原料，合成了两种新型的可聚合磷脂酰胆碱。 10与13-十四炔酸的二酰化反应，然后通过炔的氧化偶联得到32元甘油大环17。 用棕榈酸和15-十六炔酸依次酰化10，然后进行氧化偶联，得到bolaform 16，系在甘油的2位。 本文介绍了一种在二氯甲烷中用溴化二甲基硼在-78 ℃下裂解4-甲氧基苄醚的新方法。 1，3-二乙炔、1，4-二烯和酯在实验条件下是稳定的，酰基链从二级位置向一级位置的迁移被完全抑制。 然后，通过用2-氰乙基2-溴乙基N，N-二异丙基氨基亚磷酸酯进行四唑催化的亚磷酸化，氧化，并用三甲胺处理以同时置换溴并消除氰乙基，将二酰基甘油有效地转化为相应的磷脂酰胆碱。
The total synthesis of two novel polymerizable phosphatidylcholines has been accomplished using 3-(4-methoxybenzyl)-sn-glycerol 10 as starting material. Diacylation of 10 with 13-tetradecynoic acid followed by oxidative coupling of the alkynes gives the 32-membered glycerol macrocycle 17. Sequential acylation of 10 with palmitic acid and 15-hexadecynoic acid followed by oxidative coupling gives the bolaform 16, tethered at the 2-position of the glycerol. A new method for the cleavage of 4-methoxybenzyl ethers using dimethylboron bromide at -78-degrees-C in dichloromethane is described. 1,3-Diacetylenes, 1,4-dienes, and esters are stable under the experimental conditions, and the migration of acyl chains from secondary to primary positions is totally suppressed. The diacylglycerols are then efficiently converted into the corresponding phosphatidylcholines by tetrazole-catalyzed phosphitylation with 2-cyanoethyl 2-bromoethyl N,N-diisopropylamino phosphite, oxidation, and treatment with trimethylamine to simultaneously displace the bromide and eliminate the cyanoethyl group.