Synthesis of Conformationally-Locked cis- and trans-Bicyclo[4.4.0] Mono-, Di-, and Trioxadecane Modifications of Galacto- and Glucopyranose; Experimental Limiting (3)J(H,H) Coupling Constants for the Estimation of Carbohydrate Side Chain Populations and Beyond.
Synthesis of Conformationally-Locked cis- and trans-Bicyclo[4.4.0] Mono-, Di-, and Trioxadecane Modifications of Galacto- and Glucopyranose; Experimental Limiting (3)J(H,H) Coupling Constants for the Estimation of Carbohydrate Side Chain Populations and Beyond.
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构象锁定的顺式和反式 - 脱叶[4.4.0]单，二 - 二烷糖的修饰；实验限制（3）J（H，H）耦合常数，用于估计碳水化合物侧链种群及其他。
DOI：
10.1021/acs.joc.7b02891
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发表时间：
2018-01-19
期刊：
影响因子：
--
通讯作者：
Crich D
中科院分区：
文献类型：
--
作者：
Amarasekara H;Dharuman S;Kato T;Crich D
六吡喃糖侧链填充三个交错的构象，其比例可以确定从三组理想的限制3 JH 5，H6 R和3 JH 5，H6 S耦合常数结合时间平均的实验耦合常数。通过模型化合物的研究、Haasnoot-Altona和相关方程的使用或量子力学计算获得的极限耦合常数的文献值可以导致计算出的三种理想构象之一的负种群。这样的值产生的限制耦合常数和/或从人口的非理想构象的错误。我们描述了一系列的顺式和反式稠合的单，二，和三氧杂双环[4.4.0]辛烷类化合物的合成和分析。从内部模型（-CH（OR）-CH（OR）-）到终端系统（-CH（OR）-CH 2（OR））的数据应用的校正因子是从进一步模型的比较中推导出来的，并在必要时应用。限制耦合常数如此派生的应用到侧链构象的三个模型hexopyranosides，导致计算构象人口没有负值。虽然，主要是为吡喃己糖侧链开发的，限制耦合常数是合适的，与校正因子，应用于高碳糖的侧链和构象分析的无环二醇及其衍生物在更一般的意义上。
Hexopyranose side chains populate three staggered conformations, whose proportions can be determined from the three sets of ideal limiting 3JH5,H6R and 3JH5,H6S coupling constants in combination with the time-averaged experimental coupling constants. Literature values for the limiting coupling constants, obtained by the study of model compounds, the use of the Haasnoot-Altona and related equations, or quantum mechanical computations, can result in computed negative populations of one of the three ideal conformations. Such values arise from errors in the limiting coupling constants and/or from the population of non-ideal conformers. We describe the synthesis and analysis of a series of cis- and trans-fused mono-, di-, and tri-oxabicyclo[4.4.0]octane-like compounds. Correction factors for the application of data from internal models (-CH(OR)-CH(OR)-) to terminal systems (-CH(OR)-CH2(OR)) are deduced from comparison of further models, and applied where necessary. Limiting coupling constants so-derived are applied to the side chain conformations of three model hexopyranosides, resulting in calculated conformer populations without negative values. Although, developed primarily for hexopyranose side chains, the limiting coupling constants are suitable, with the correction factors presented, for application to the side chains of higher carbon sugars and to conformation analysis of acyclic diols and their derivatives in a more general sense.
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影响因子：
5.2
作者：
Crich D;Sharma I
通讯作者：
Sharma I
影响因子：
2.7
作者：
Bols M;Pedersen CM
通讯作者：
Pedersen CM
影响因子：
3.1
作者：
Bohe, Luis;Crich, David
通讯作者：
Crich, David
影响因子：
3.6
作者：
Dhakal, Bibek;Buda, Szymon;Crich, David
通讯作者：
Crich, David
DOI：
10.1039/a705275h
发表时间：
1998-01-07
期刊：
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1
影响因子：
--
作者：
Douglas, NL;Ley, SV;Warriner, SL
通讯作者：
Warriner, SL