Molecular recognition. 15. Molecular recognition and stereoselectivity: geometrical requirements for the multiple hydrogen-bonding interaction of diols with a multidentate polyhydroxy macrocycle
Molecular recognition. 15. Molecular recognition and stereoselectivity: geometrical requirements for the multiple hydrogen-bonding interaction of diols with a multidentate polyhydroxy macrocycle
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分子识别。
DOI：
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发表时间：
1991
期刊：
影响因子：
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通讯作者：
Y. Aoyama
中科院分区：
文献类型：
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作者：
Y. Kikuchi;Y. Kato;Yasutaka Tanaka;H. Toi;Y. Aoyama
间苯二酚十二醛环四聚物1在氯化镉溶液中与环己二醇、2，4-戊烷和2，5-己二醇作为开链类似物与环己醇、顺、反-4-叔丁基环已醇形成氢键1/1的络合物。环状二醇与1的亲和力明显大于开链二醇和一元醇。环己二醇的区域异构体和立体异构体的立体选择性取决于所涉及的两个羟基的构型(轴-赤道)和相对位置(1，4>；1，2>；1，3)，并以cis-1，4>；cis-1，2>；trans-1，3>；trans-1，4>；cis-1，3>；trans-1，2；的顺序递减。因此，立体选择性为顺-1，4/反-1，4=8.0，顺-1，2/反-1，2=2.5，和反-1，3/顺-1，3=1.5。根据二元醇和1，2，4-二元醇的多重氢键讨论了二元醇结合的选择性。
Resorsinol-dodecanal cyclotetramer 1 in CDCl 3 forms hydrogen-bonded, 1/1 complexes with cyclohexanediols as well as with 2,4-pentane- and 2,5-hexanediol as their open-chain analogues and cyclohexanol and cis- and trans-4-tert-butylcyclohexanol. The affinities to 1 of cyclic diols are significantly larger than those of open-chain diols and monools. Those of regio- and stereoisomers of cyclohexanediol depend on the configuration (axial-equatorial>diequatorial) and relative positions (1,4>>1,2>1,3) of the two OH groups involved and decrease in the order cis-1,4>cis-1,2>trans-1,3>trans-1,4>cis-1,3>trans-1,2; the stereoselectivities are thus cis-1,4/trans-1,4=8.0, cis-1,2/trans-1,2=2.5, and trans-1,3/cis-1,3=1.5. The selectivities in the diol binding are discussed in terms of multiple hydrogen bonding of diol and 1