Selfassembly of Molecules in Crystal and Its Application to Selective Synthesis

晶体分子自组装及其在选择性合成中的应用

• 批准号: 03303002
• 负责人: TODA Fumio
• 金额: $ 6.21万
• 依托单位: Ehime University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Co-operative Research (A)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-03303002/
• 关键词: inclusion crystal; chiral recognition; optical resolution; ammonium salt; bis-beta-naphthol; bisphenanthrol; hydrogen bond; chiral shift reagent; アンモニウム塩ホスト; ビス-β-ナフトール; 包接体結晶; 固相反応; ホストーゲスト錯体; 不斉合成; 不斉発現; クリスタルエンジニアリング; 光学活性ホスト

Application of the chiral recognition in a host-quest inclusion crystal to optical resolution of the guest compound is successful. The optically active host compounds which were derived from tartaric acid were found to be effective for optical resolution of various guest compounds. Chiral recognition by the optically active diacetylenic alcohol host compound depends delicatelly on its chemical structure. For example, although the optically active diacetylenic alcohol host is not effective for the resolution of an important starting material of prostaglandin synthesis, hydroxycyclopentenone, the diacetylenic alcohol host compound which has p-disubstituted phenyl group between the two acetylenic groups works very well for the resolution.However, alkaloid such as brucine was found to be effective for the resolution of benzhydrol derivatives. Interestingly, the benzhydrol which has a substituent on meta- or para-position of one phenyl group,was resolved efficiently by complexation with bru … More cine. However, the benzhydrol which has an ortho-substituent was not. The structure dependence in the chiral recognition seems to be relating to so called the ortho-effect in organic chemistry in solution.The most interesting finding is the chiral recognition with cinchonidium chloride host. N-Benzoylcinchonidium chloride formed a 1:1 inclusion crystal with 2,2'-dihydroxy-1,1'-binaphthyl. By using the complexation, the latter was resolved very effectively. X-ray crystal structure analysis of the inclusion crystal showed that the hydroxyl group of the binaphthol forms a hydrogen bond network with the chloride anion. Interestingly, the N-benzylcinchonidium chloride was not effective for 10,10'-dihydroxy-9,9'-biphenanthryl which was, however, resolved easily by complexation with N-butylcinchonidium chloride.Some fruitful results were obtained in the study of enantioselective reaction in inclusion crystal. For example, photoirradiation of cyclohexenone and coumarin in their inclusion crystal with an optically active host compound gave optically active dimer. Photoirradiation of an inclusion crystal of acrylanilide with an optically active host gave optically active dihydroquinolinone derivative. The enantioselectivity of these photoreactions in inclusion crystals is almost perfect and optically almost pure enantiomers were obtained. Enantioselective Michael reaction in inclusion crystal was also successful.It was also disclosed that most chiral hosts work as chiral shift reagents. Less

将主-客体包结晶体中的手性识别应用于客体化合物的光学拆分是成功的。酒石酸衍生的光学活性主体化合物被发现对各种客体化合物的光学拆分是有效的。手性识别的光学活性二炔醇主体化合物微妙地依赖于它的化学结构。例如，虽然光学活性的二炔醇主体对于前列腺素合成的重要起始原料羟基环戊烯酮的拆分无效，但是在两个炔基之间具有对-二取代苯基的二炔醇主体化合物对于拆分非常有效，然而，生物碱如马钱子碱被发现对于二苯甲醇衍生物的拆分有效。有趣的是，在一个苯基的Meta位或对位上具有取代基的二苯甲醇可以通过与Bru络合而有效地拆分。 ...更多信息 电影。然而，具有邻位取代基的二苯甲醇不是。手性识别的结构依赖性与有机化学中的邻位效应有关，最有趣的发现是与氯化金鸡纳碱主体的手性识别。N-苯甲酰基氯化金鸡纳铵与2，2 '-二羟基-1，1'-联萘形成1：1包结晶体。采用络合作用，后者得到了很好的解决。X射线晶体结构分析表明，联萘烷的羟基与氯离子形成氢键网络。有趣的是，氯化苄基金鸡纳铵对10，10 ′-二羟基-9，9 ′-联菲不起作用，而氯化丁基金鸡纳铵则能很好地拆分10，10 ′-二羟基-9，9 ′-联菲。例如，光照射环己烯酮和香豆素与光学活性主体化合物的包合晶体得到光学活性二聚体。在光辐射下，丙烯酰苯胺与光学活性主体包结得到了光学活性的二氢喹啉酮衍生物。在包合晶体中，这些光反应的对映选择性几乎是完美的，得到了光学纯的对映体。在包合晶体中也成功地进行了对映选择性Michael反应，并揭示了大多数手性主体作为手性位移试剂的作用。少

项目成果

Koichi Tanaka: "Control of the Stereochemistry in the Photocyclisation of Acrylanilides to 3,4-Dihydroquinolin-2(1H)-ones" J. Chem. Soc., Chem. Commun.1053-1054 (1992)

Koichi Tanaka：“控制丙烯酰苯胺光环化为 3,4-二氢喹啉-2(1H)-酮的立体化学”J. Chem。

Fumio Toda: "Inclusion Complexation of Cholestanol, Cholesterol, Sitosterol, Stigmasterol, and Ergaosterol with Various Guests" Bull. Chem. Soc. Jpn.66. 320-323 (1993)

Fumio Toda：“胆固醇、胆固醇、谷甾醇、豆甾醇和麦角甾醇与各种客体的包合络合”公牛。

F.Toda,: "Optical Resolution of Bicyclo〔2.2.1〕heptanone, Bicyclo〔2.2.2〕octanone, and Bicyclo〔3.2.1〕octanone Derivatives by Inclusion Complexation with Optically Active Host" J.Org.Chem.56. 7332-7335 (1991)

F.Toda，：“通过与光学活性主体包合络合对双环[2.2.1]庚酮、双环[2.2.2]辛酮和双环[3.2.1]辛酮衍生物进行光学拆分”J.Org.Chem.56。 7332-7335 (1991)

F.Toda: "Inclusion Compounds Vo1.4" Oxford University Press, 511 (1991)

F.Toda：“包合物 Vo1.4”牛津大学出版社，511 (1991)

Fumio Toda: "Photocyclisation of Phenylglyoxylamides as Inclusion Complexes with an Optically Active Host Derived from Tartaric Acid" J. Chem. Soc. Perkin Trans. 1. 1461-1462 (1992)

Fumio Toda：“苯乙醛酰胺与酒石酸衍生的光学活性主体作为包合物的光环化”J. Chem。