公开(公告)号：KR100915095B1

公开(公告)日：2009-09-02

申请号：KR1020080006571

申请日：2008-01-22

Applicant: 성균관대학교산학협력단

Inventor： 윤재숙 ,  이지언 ,  권지숙

IPC: C07F5/02

Abstract: 본 발명은 전이금속촉매인 구리를 이용한 알파, 베타-알킨 에스터 화합물 (α,β-alkyne ester compound)의 β-보론화 방법에 관한 것으로, 하기 반응식 (1)에 나타낸 바와 같이 구리 촉매 및 포스핀리간드의 존재 하에서, 용매 중 화학식 (I)의 알파, 베타-알킨 에스터 화합물과 화학식 (II)의 비스피나콜라토다이보론을 반응시켜 화학식 (III)의 β-위치에 보론이 첨가된 알켄 에스터 (alkene ester)를 제조하는 방법에 관한 것이다. 본 발명의 제조방법은 다양한 알파, 베타-알킨 에스터 화합물에 선택적으로 β-위치에 피나콜보론 에스터를 첨가할 수 있으며, 이로부터 β-보론이 첨가된 알켄 화합물의 제조와 그 생성물의 응용이 가능하다. 따라서, 본 발명에 의해 생성된 화학식(III)의 화합물은 유기합성의 관점에서 새로운 탄소-탄소 결합반응 또는 다른 작용기로의 변환이 가능하여 유용한 중간체로 쓰일 수 있다.
반응식 1

상기 식에서,
R
1 및 R
2
는 명세서에 기재된 바와 같다.

公开(公告)号：KR1020090080677A

公开(公告)日：2009-07-27

申请号：KR1020080006571

申请日：2008-01-22

Applicant: 성균관대학교산학협력단

Inventor： 윤재숙 ,  이지언 ,  권지숙

IPC: C07F5/02

CPC classification number: C07F5/025 ,  B01J27/122

Abstract: A beta-boration of alpha,beta-alkyne ester compound is provided, which enables selective beta-boration under the presence of copper catalyst, phospine ligand and alcohol. A beta-boration method of alpha,beta-alkyne ester compound comprises a step of reacting bispinacolato diboron of the chemical formula (II) with alpha,beta-alkyne ester compound of the chemical formula (I) in solvent under the presence of copper catalyst and phospine ligand to produce alkene ester compound in which a boron is added on beta-site of the chemical formula (III). In the chemical formula (I) and (III), R1 is hydrogen, C1-C10 alkyl, phenyl or substituted or non-substituted C6-C14 aromatic family. R2 is C1-C6 alkyl, phenyl or substituted C6-C14 aromatic family. The phospine ligand is a ligand selected from a group of xantphos, DPE phos, and dppf. The use amount of the bispinacolato diboron of the chemical formula (II) is under 1.1 equivalent.

Abstract translation: 提供α，β-炔烃酯化合物的β-硼酸酯化合物，其可以在铜催化剂，磷酸配体和醇的存在下进行选择性的β-硼酸化。 α，β-炔烃酯化合物的β-硼酸化方法包括使化学式（II）的双扁桃螺酚二硼酸与化学式（I）的α，β-炔烃酯化合物在溶剂中在铜催化剂存在下反应的步骤 和磷酸配体以制备其中在化学式（III）的β-位上加入硼的烯酯化合物。 在化学式（I）和（III）中，R 1是氢，C 1 -C 10烷基，苯基或取代或未取代的C 6 -C 14芳族。 R2是C1-C6烷基，苯基或取代的C6-C14芳族。 膦配体是选自呫吨，DPE磷和dppf组的配体。 化学式（II）的双拼扣多巴因的使用量低于1.1当量。

公开(公告)号：KR100809848B1

公开(公告)日：2008-03-04

申请号：KR1020060114510

申请日：2006-11-20

Applicant: 성균관대학교산학협력단

Inventor： 윤재숙 ,  문성윤 ,  이지언

IPC: C07F5/02

CPC classification number: C07F5/025 ,  B01J27/122 ,  B01J31/2208 ,  B01J2531/16

Abstract: A method for preparing a beta-boronated alpha,beta-unsaturated carbonyl compound is provided to beta-boronate the alpha,beta-unsaturated carbonyl compound efficiently, thereby being applied to prepare boron added compounds at various beta positions and being useful for forming a product in an aspect of BNCT(boron neutron capture therapy). A method for preparing a compound where a boron is added at a beta position comprises a step of reacting an alpha,beta-unsaturated carbonyl compound represented by the formula(1) with a diboronate compound at a temperature of 25-50 deg.C in a solvent such as dimethyl formamide, toluene and tetrahydrofuran in the presence of a Cu catalyst such as CuCl/NaOt-Bu, Cu(OAc) and CuOtBu, a base, and a phosphine ligand or a C1-6 primary to tertiary alcohol. In the formula(1), R is H, C1-10 alkyl, phenyl, substituted or unsubstituted C6-14 aromatic, or C6-12 hetero aromatic including at least one N and O; R' is H or C1-10 alkyl; and EWG is ketone or ester. Further, a ligand selected from Xantphos, DPEphos, Tributylphosphine and Tricyclohexylphosphine is additionally added when reacting.

Abstract translation: 提供了制备β-硼化的α，β-不饱和羰基化合物的方法，以有效地对α，β-不饱和羰基化合物进行β-硼酸化，从而应用于在各种β位置制备加入硼的化合物并且可用于形成产物 在BNCT（硼中子俘获治疗）的一个方面。 制备其中在β位置添加硼的化合物的方法包括使式（1）表示的α，β-不饱和羰基化合物与二硼酸酯化合物在25-50℃温度下反应的步骤 溶剂如二甲基甲酰胺，甲苯和四氢呋喃，在Cu催化剂如CuCl / NaOt-Bu，Cu（OAc）和CuOtBu，碱和膦配体或C1-6伯醇与叔醇的存在下反应。 在式（1）中，R为H，C 1-10烷基，苯基，取代或未取代的C 6-14芳族或C 6-12杂芳族，包括至少一个N和O; R'是H或C 1-10烷基; 而EWG是酮或酯。 此外，当反应时另外加入选自Xantphos，DPEphos，三丁基膦和三环己基膦的配体。