Chiral Lewis Acids with Two Boron Centers
具有两个硼中心的手性路易斯酸
基本信息
- 批准号:08651006
- 负责人:
- 金额:$ 1.54万
- 依托单位:
- 依托单位国家:日本
- 项目类别:Grant-in-Aid for Scientific Research (C)
- 财政年份:1996
- 资助国家:日本
- 起止时间:1996 至 1997
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
A chiral bimetallic Lewis acid, 2,2'-(1,2-phenylene)bis[(4R,5R)-4,5-diphenyl-1,3,2-dioxaborolane](1), has been synthesized. The exceptionally strong binding of 1 with benzylamine was demonstrated by titrations. The complex formation ratio of 1 : amine=1 : 2 was determined by a Job plot. The binding constants, K_1 and K_2, were determined by non-linear curve fitting to be K_1<<K_2. The results can be explained in terms of an allosteric effect. The first amine molecule coordinates with one of the two boron atoms of 1 ; at the same time, one NH proton interacts with one of the two oxygen atoms in the other dioxaborolane ring to form a hydrogen bond. As a result, the two dioxaborolane rings are conformationally fixed by two-point binding to provide a preferable binding site for the second amine molecule. Although only a small chiral recognition of 1-phenylethylamine has been obtained with 1, the clear separation of the peaks of the amine provides the possibility to use 1 as an NMR chiral-shift reagent.In the presence of another chiral bimetallic Lewis acid, 2,2'-{(1R,2R)-1,2-ethylene}bis(4-aryl-1,3,2-dioxaborolan-5-one)(2), acetophenone and its derivatives were reduced by LiBH_4, in moderate to good ee's(up to 99% ee). Amino group in the substrates affected on the enantioselectivities.
合成了一种手性手性刘易斯酸2,2 ′-(1,2-亚苯基)双[(4 R,5 R)-4,5-二苯基-1,3,2-二氧硼杂环戊烷](1)。通过滴定证明了1与苄胺的异常强的结合。通过Job图确定1:胺=1:2的络合物形成比。用非线性曲线拟合法测得结合常数K_1和K_2为K_1<<K_2。结果可以用变构效应来解释。第一个胺分子与1的两个硼原子之一配位;同时,一个NH质子与另一个二氧硼杂环戊烷环中的两个氧原子之一相互作用形成氢键。结果,两个二氧杂硼杂环戊烷环通过两点结合在构象上固定,从而为第二胺分子提供优选的结合位点。虽然1与1-苯乙胺只有很小的手性识别,但胺峰的清晰分离提供了将1用作NMR手性位移试剂的可能性。(4-芳基-1,3,2-二氧硼戊环-5-酮)(2)、苯乙酮及其衍生物用LiBH_4还原,ee值可达99%ee。底物中的氨基对映体选择性有影响。
项目成果
期刊论文数量(4)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
野崎 京子: "Chiral Bimetallic Boronic Esters : A Donor-Acceptor Coexisting Receptor for Amines" Bull.Chem.Soc.Jpn.69. 2043-2052 (1996)
Kyoko Nozaki:“手性双金属硼酸酯:胺的供体-受体共存受体”Bull.Chem.Soc.Jpn.69 (1996)。
- DOI:
- 发表时间:
- 期刊:
- 影响因子:0
- 作者:
- 通讯作者:
野崎 京子: "Chiral Bimetalilic Bororvic Esters : A Donor-Acceptor Coexisting Receptor for Amines" Bull. Chem, Soc,Jpn. 69. 2043-2052 (1996)
Kyoko Nozaki:“手性双金属 Bororvic 酯:胺的供体-受体共存受体”Bull,Chem,Soc,Jpn. 69。2043-2052 (1996)
- DOI:
- 发表时间:
- 期刊:
- 影响因子:0
- 作者:
- 通讯作者:
K.Nozaki: "Chiral Bimetallic Boronic Esters ; A Donor-Acceptor Coexisting Receptor for Amines" Bull.Chem.Soc.Jpn.vol.69. 2043-2052 (1996)
K.Nozaki:“手性双金属硼酸酯;胺的供体-受体共存受体”Bull.Chem.Soc.Jpn.vol.69。
- DOI:
- 发表时间:
- 期刊:
- 影响因子:0
- 作者:
- 通讯作者:
K.NOZAKI: "Chiral Bimetallic Boronic Esters:A Donor-Acceptor Coexisting Receptor for Amines" Bull.Chem.Soc.Jpn.69. 2043-2052 (1996)
K.NOZAKI:“手性双金属硼酸酯:胺的供体-受体共存受体”Bull.Chem.Soc.Jpn.69。
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- 发表时间:
- 期刊:
- 影响因子:0
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NOZAKI Kyoko其他文献
NOZAKI Kyoko的其他文献
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