Efficient Synthesis of 2-Ethyl-A-ring Analogues of 19-Nor-1α,25-dihydroxy Vitamin D_3

The novel 19 nor l α ,25 dihydroxy vitamin D 3 analogues possessing an ethyl at the 2 position(4 and 5), were synthesized by coupling 25 hydroxy Windaus Grundmann ketone derivative 20 with A ring synthons(15 and 19) respectively. The enantioselective synthesis of substituted bicyclic hexanes structure A ring synthons, started from all cis 3,5 dihydroxy 4 ethyl 1 (methoxycarbonyl)cyclohexane via lipase catalyzd asymmetrization, was demonstrated.

Porous 3D carbon-based materials:An emerging platform for efficient hydrogen production

Due to their unique properties and uninterrupted breakthrough in a myriad of clean energy-related applications,carbon-based materials have received great interest.However,the low selectivity and poor conductivity are two primary difficulties of traditional carbon-based materials(zero-dimensional(0D)/one-dimensional(1D)/two-dimensional(2D)),enerating inefficient hydrogen production and impeding the future commercialization of carbon-based materials.To improve hydrogen production,attempts are made to enlarge the surface area of porous three-dimensional(3D)carbon-based materials,achieve uniform interconnected porous channels,and enhance their stability,especially under extreme conditions.In this review,the structural advantages and performance improvements of porous carbon nanotubes(CNTs),g-C_(3)N_(4),covalent organic frameworks(COFs),metal-organic frameworks(MOFs),MXenes,and biomass-derived carbon-based materials are firstly summarized,followed by discussing the mechanisms involved and assessing the performance of the main hydrogen production methods.These include,for example,photo/electrocatalytic hydrogen production,release from methanolysis of sodium borohydride,methane decomposition,and pyrolysis-gasification.The role that the active sites of porous carbon-based materials play in promoting charge transport,and enhancing electrical conductivity and stability,in a hydrogen production process is discussed.The current challenges and future directions are also discussed to provide guidelines for the development of next-generation high-efficiency hydrogen 3D porous carbon-based materials prospected.

Stereochemistry Control in Direct 1α-Hydroxylation of 5,6-trans-Vitamin D_(3) by Solid Support

A solid-phase synthesis of 1α-hydroxylation of 5,6-trans-vitamin D3 8 is described.The solid phase resin acts as a special protecting group, which gives a higher stereoselectivity in oxidation step than classical protecting groups. The stereochemistry control is favored by using high crosslinkage polymer support in a poor solvent. This work may be of benefit to the synthesis of vitamin D system.

Improved and efficient synthesis of Maxacalcitol

Maxacalcitol,the 22-oxa-derivative of 1a,25-dihydroxyvitamin D3,has been used as an antihyperparathyroidism and antipsoriatic drug.In this paper,an alternative synthetic route has been developed using commercially available vitamin D2as the starting material.In addition,as a key intermediate,the asymmetric synthesis of 20（S）-alcohol 14 with the chiral auxiliary（R-CBS） was described for the first time.This new synthetic route afforded Maxacalcitol with improved overall yield（13.9%） in eleven steps.

维生素D_3合成新工艺的初步设想

维生素D3 在医药及临床上有许多重要的应用 ,其目前都是由 7-脱氢胆固醇通过光照反应而得。综述了 7-脱氢胆固醇的制备方法 ,包括两种化学法———溴化 /脱溴化氢法和氧化还原消除法。由胆固醇的生物合成全过程 ,综述采用生物化学法合成 7-脱氢胆固醇的研究 ,提出几种生物法合成 7-脱氢胆固醇的构想 :①角鲨烯或是羊毛甾醇酶法转化 ;②麦角固醇生产菌的改造或是采用基因工程的方法 ;③胆固醇经脱氢酶脱氢转化 ;

几种双噻吩[3,2-b:2',3'-d]并吡咯类有机导电材料中间体的合成、表征

以3,4’-二溴-(2,5’)-联二噻吩为原料,采用偶联、溴代、取代等反应合成了几种新型二噻吩[3,2-b:2’,3’-d]并吡咯类有机导电材料中间体,通过红外光谱、核磁共振谱对其结构进行了表征.