公开(公告)号：KR100542868B1

公开(公告)日：2006-01-20

申请号：KR1020030063730

申请日：2003-09-15

Applicant: 한국과학기술연구원

Inventor： 이상기 ,  이재균 ,  장용건 ,  이정근

IPC: C07F9/6503

Abstract: 본 발명은 하기 화학식 1로 표시되는 이미다졸 염을 포함하는 키랄 비스포스핀에 전이금속이 배위된 전이금속착물, 이의 중간체 화합물 및 상기 전이금속착물의 제조방법에 관한 것이다.


(상기 화학식 1에서, n은 1~10의 정수이며, R
1 , R
2 , R
3 , R
4 는 서로 독립적이며, 수소, C
1 -C
10 알킬, C
3 -C
8 고리화 알킬, 아릴기 또는 치환된 아릴기를 나타내며, 이때 치환체는 할로겐, C
1 -C
6 알킬기 또는 C
1 -C
6 의 알콕시기이다.
Ar은 페닐 또는 치환된 아릴기를 나타내며, 이때 치환체는 할로겐, C
1 -C
6 알킬 또는 C
1 -C
6 의 알콕시기이다.
X는 BF
4 , PF
6 , SbF
6 , OTf, NTf
2 이다.)
본 발명의 키랄 비스포스핀은 전이금속이온과 키랄 금속착물을 형성하여, 청정용매인 이온성 액체 내에서 비대칭 촉매화 수소 환원 반응시 촉매로 작용하여 반응성이 크고, 광학선택성 및 전환율이 우수하며, 반응 후 촉매의 분리 및 회수가 용이하다.

公开(公告)号：KR1020050027453A

公开(公告)日：2005-03-21

申请号：KR1020030063730

申请日：2003-09-15

Applicant: 한국과학기술연구원

Inventor： 이상기 ,  이재균 ,  장용건 ,  이정근

IPC: C07F9/6503

CPC classification number: C07F19/00 ,  C07D233/14 ,  C07F9/5045 ,  C07F9/6506 ,  C07F15/008

Abstract: Chiral bisphosphine bearing imidazolium salt, their intermediates and a preparation method thereof are provided, which chiral bisphosphine forms chiral metal complex with transition metal ion, has high reactivity during asymmetric hydrogen reaction in ionic liquid, and improved photo-selectivity and conversion rate, and easily isolated and recovered after reaction. The chiral bisphosphine bearing imidazolium salt represented by formula (1) is provided, wherein n is an integer of 1 to 10; R1, R2, R3 and R4 are independently hydrogen, C1-C10 alkyl, C3-C8 cyclic alkyl, aryl or substituted aryl in which the substituent is halogen, C1-C6 alkyl or C1-C6 alkoxy; Z is phenyl or substituted aryl in which the substituent is halogen, C1-C6 alkyl or C1-C6 alkoxy; and X is BF4, PF6, SbF6, OTf or NTf2. The intermediates of the chiral bisphosphine bearing imidazolium salt represented by formula (1) are represented by formula (2), formula (3), formula (4), formula (5) and formula (6), respectively, wherein Y2 is halogen, methane sulfonyl or para-toluenesulfonyl.

Abstract translation: 提供手性双膦咪唑鎓盐及其制备方法，其中手性双膦与过渡金属离子形成手性金属络合物，在离子液体不对称氢反应中具有高反应性，并提高了光选择性和转化率 反应后分离并回收。 提供由式（1）表示的含有手性双膦的咪唑鎓盐，其中n为1至10的整数; R1，R2，R3和R4独立地是氢，C1-C10烷基，C3-C8环烷基，其中取代基是卤素的芳基或取代的芳基，C1-C6烷基或C1-C6烷氧基; Z是其中取代基是卤素，C 1 -C 6烷基或C 1 -C 6烷氧基的苯基或取代的芳基; X为BF4，PF6，SbF6，OTf或NTf2。 由式（1）表示的含有手性双膦的咪唑鎓盐的中间体分别由式（2），式（3），式（4），式（5）和式（6）表示，其中Y2是卤素， 甲磺酰或对甲苯磺酰。

公开(公告)号：KR100425526B1

公开(公告)日：2004-03-30

申请号：KR1020010011252

申请日：2001-03-05

Applicant: 한국과학기술연구원

Inventor： 이상기 ,  이재균 ,  장용건

IPC: C07F9/645 ,  C01G23/00

Abstract: PURPOSE: Provided are chiral diphosphine compounds which form a metal complex with transition metal thus have excellent optical selectivity and transition rate, and a manufacturing method of chiral compounds by applying them as metal catalyst in asymmetric reactions. CONSTITUTION: The chiral diphosphine compound is represented by the formula(1), wherein X, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R10 and R11 are as defined in the description. It is characteristically manufactured by a compound of the formula(7) with an organophosphine-based metallic salt of the formula(8) in the presence of organic solvents.

Abstract translation: 目的：提供与过渡金属形成金属配合物的手性二膦化合物因此具有优异的光学选择性和转变速率，以及通过在不对称反应中将它们用作金属催化剂的手性化合物的制备方法。 构成：手性二膦化合物由式（1）表示，其中X，R 1，R 2，R 3，R 4，R 5，R 6，R 7，R 8，R 9，R 10，R 10和R 11如说明书中所定义。 它是由式（7）化合物与式（8）的有机膦基金属盐在有机溶剂存在下特征制造的。

公开(公告)号：KR1020020071245A

公开(公告)日：2002-09-12

申请号：KR1020010011252

申请日：2001-03-05

Applicant: 한국과학기술연구원

Inventor： 이상기 ,  이재균 ,  장용건

IPC: C07F9/645 ,  C01G23/00

CPC classification number: C07F9/6506 ,  B01J31/24 ,  B01J2231/321

Abstract: PURPOSE: Provided are chiral diphosphine compounds which form a metal complex with transition metal thus have excellent optical selectivity and transition rate, and a manufacturing method of chiral compounds by applying them as metal catalyst in asymmetric reactions. CONSTITUTION: The chiral diphosphine compound is represented by the formula(1), wherein X, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R10 and R11 are as defined in the description. It is characteristically manufactured by a compound of the formula(7) with an organophosphine-based metallic salt of the formula(8) in the presence of organic solvents.

Abstract translation: 目的：提供与过渡金属形成金属络合物的手性二膦化合物，因此具有优异的光学选择性和转变速率，以及手性化合物的制备方法，通过将其用作不对称反应中的金属催化剂。 构成：手性二膦化合物由式（1）表示，其中X，R 1，R 2，R 3，R 4，R 5，R 6，R 7，R 8，R 9，R 10，R 10和R 11如说明书中所定义。 其特征在于，在有机溶剂的存在下，由式（7）的化合物与式（8）的有机膦系金属盐制造。