• 제목/요약/키워드: Chiral catalyst

검색결과 52건 처리시간 0.025초

폴리머 키랄 살렌을 함유한 메조세공 모더나이트의 비대칭 촉매 활성 (Asymmetric Catalytic Activity of Mesoporous Mordenite containing Polymeric Chiral Salen Complexes in the Mesopore System)

  • 곽소봉;김용석;라울;김건중
    • 공업화학
    • /
    • 제20권3호
    • /
    • pp.279-284
    • /
    • 2009
  • 모더나이트결정 중의 실리카를 제어된 알칼리용액의 처리로 추출제거하여 중간세공이 형성되도록 하였다. 형성된 중간세공의 크기는 알칼리용액의 농도를 변화시킴으로써 조절할 수 있었다. 알칼리처리 후의 모더나이트 제올라이트 내부의 세공구조를 조사하였다. 새둥지형태의 중간세공을 형성시키기 위해서는, 알칼리용액 처리전에 모더나이트결정의 바깥표면을 티타니아로 코팅하는 것이 가장 효과적임을 관찰하였다. 모더나이트 내부의 중간세공에 고분자형의 코발트(III) 살렌착체를 "ship-in-a-bottle"법으로 가둔 촉매를 제조하였다. 이 고정화촉매를 물에 의한 에피클로로히드린의 산소고리열림반응에 사용하여, 촉매반응에서 높은 수율과 광학선택성을 얻을 수 있었다.

Highly Efficient Microwave-assisted Aminolysis of Epoxides in Water

  • Zuo, Hua;Li, Zhu-Bo;Zhao, Bao-Xiang;Miao, Jun-Ying;Meng, Li-Juan;Jang, Ki-Wan;Ahn, Chul-Jin;Lee, Dong-Ha;Shin, Dong-Soo
    • Bulletin of the Korean Chemical Society
    • /
    • 제32권spc8호
    • /
    • pp.2965-2969
    • /
    • 2011
  • Highly efficient and rapid aminolysis of epoxides with various amines in water under microwave irradiation in the absence of catalyst was developed. Chiral ${\beta}$-amino alcohols were formed in a short time with excellent yields.

Fabrication of Hollow Metal Microcapsules with Mesoporous Shell Structure: Application as Efficient Catalysts Recyclable by Simple Magnetic Separation

  • Jang, Da-Young;Jang, Hyung-Gyu;Kim, Gye-Ryung;Kim, Geon-Joong
    • Bulletin of the Korean Chemical Society
    • /
    • 제32권9호
    • /
    • pp.3274-3280
    • /
    • 2011
  • Monodispersed porous NiO and $Co_3O_4$ microcapsules with a hollow core were synthesized using SBA-16 silica sol and PS as a hard template. The porous hollow microcapsules were characterized by XRD, TEM and $N_2$ adsorption/desorption analysis. After $H_2$ reduction of metal oxide microspheres, they were conducted as an active catalyst in the reduction of chiral butylronitrile and cyanobenzene. The mesoporous metals having a hollow structure showed a higher activity than a nonporous metal powder and an impregnated metal on the carbon support.

Diastereoselective Synthesis of anti-1,2-Aminoalcohol by Palladium(II) Catalyzed Aza-Claisen Rearrangement

  • Yoon, Youn-Jung;Chan, Myung-Hee;Joo, Jae-Eun;Kim, Yong-Hyun;Oh, Chang-Young;Lee, Kee-Young;Lee, Yiu-Suk;Ham, Won-Hun
    • Archives of Pharmacal Research
    • /
    • 제27권2호
    • /
    • pp.136-142
    • /
    • 2004
  • In this study, a highly diastereoselective synthesis of anti-1 ,2-aminoalcohol was explored starting from L-amino acids as chiral sources. The higher yield and diastereoselectivity was shown when the aza-Claisen rearranqement was performed with allylic trichloroacetimidate 6a in the presence of palldium(II) catalyst.

Diastereomeric Strain-Promoted Azide-Alkyne Cycloaddition: determination of configuration with the 2D NMR techniques

  • Hye Jin Jeong
    • 한국자기공명학회논문지
    • /
    • 제27권2호
    • /
    • pp.10-15
    • /
    • 2023
  • The Strain-Promoted Azide-Alkyne Cycloaddition (SPAAC) is a powerful method for synthesizing triazoles, even under physiological conditions, without a copper catalyst. This technique provides an efficient means for everyone to synthesize complex triazole derivatives rapidly. In order to investigate the configuration of triazole derivatives using bicyclo[6.1.0.]-nonyne (BCN) and chiral azide, it is necessary to employ the 2D NMR. Both 1D and 2D NMR (COSY, HSQC, 15N HMBC) are used to analyze the complex triazole product containing cyclooctyne, a diastereomeric product. The stereometric difference of the proton bonded to the same carbon is determined through the HSQC assignment. The intriguing splitting pattern of carbon resonances also reveals their diastereomeric configuration and will aid in further research based on physiological knowledge.

Highly Efficient Synthesis of Conformationally Fixed Bicyclo[3.1.0]hexyl Nucleosides with an Ethenyl Group at C3'-Position as Potential Antiviral Agents

  • Kim, Seong Jin;Woo, Youngwoo;Park, Ah-Young;Kim, Hye Rim;Son, Sujin;Yun, Hwi Young;Chun, Pusoon;Moon, Hyung Ryong
    • Bulletin of the Korean Chemical Society
    • /
    • 제35권9호
    • /
    • pp.2649-2654
    • /
    • 2014
  • Synthesis of north-5'-methylbicyclo[3.1.0]hexyl adenine and hypoxanthine nucleosides with an ethenyl group at C3' position was successfully achieved by a highly facile method. Methylbicyclo[3.1.0]hexanone (${\pm}$)-7 with three contiguous chiral centers and its epimer (${\pm}$)-6 was remarkably simply constructed only by four steps involving a carbenoid insertion reaction in the presence of rhodium (II) acetate dimer as a metal catalyst, giving a correct relative stereochemistry of the generated three chiral centers. Due to steric hindrance from the concave face of the bicyclo[3.1.0]hexanone system, a Grignard reaction of (${\pm}$)-7 with ethenylmagnesium bromide showed exclusive diastereoselectivity towards the b-face. The Grignard reaction chemoselectively proceeded without reacting with ester functionality. Coupling reaction of glycosyl donor (${\pm}$)-11 with 6-chloropurine nucleobase afforded only the desired $N^9$-alkylated nucleoside without the formation of $N^7$-regioisomer. By the conventional method, 6-chloro group was converted into 6-amino and 6-hydroxy groups to give the desired adenine and hypoxanthine bicyclo[3.1.0]hexyl carbanucleosides with 3'-ethenyl group, respectively.

초음파 조사에 의한 에폭사이드 비대칭 고리열림 반응의 속도 증진 효과 (Accelerating Effects of Ultrasonic Irradiation on Reaction Rates for the Asymmetric Ring Opening Reaction of Epoxides)

  • 이예원;박근우;김건중
    • 공업화학
    • /
    • 제30권3호
    • /
    • pp.365-370
    • /
    • 2019
  • 본 연구에서는 키랄 코발트 살렌 촉매 존재 하에서 에폭사이드 화합물의 비대칭 고리 열림 반응(EKR)에 미치는 초음파 조사 효과를 기존의 기계적 교반법과 비교하여 고찰하였다. 촉매의 활성을 비교하기 위하여 $AlCl_3,\;BF_3$ 및 니트로벤젠술폰산(NBSA)이 결합된 키랄 코발트 살렌을 합성 사용하였으며, 반응물로는 에피클로로히드린(ECH), 에폭시페녹시프로판(EPP) 및 프로필렌 옥사이드(PO)를 친핵체로는 물과 메탄올을 각각 사용하여 EKR 반응을 수행하였다. 이 반응에서 반응물을 혼합시키는 조작의 일환으로써 초음파를 반응계에 적용한 경우가 통상의 기계적인 교반보다 반응속도를 현저히 증가시키는 결과를 나타내었다. 최고의 거울상 이성체 과잉도 값인 99 ee%를 얻는데 요하는 반응시간은 초음파를 적용하였을 때가 격렬한 물리적 교반을 행한 경우보다 60% 이상 단축되었으며, 이는 용액 중에서 발생하는 초음파의 공동화 현상에 의해 형성된 강한 전단력에 의한 결과로 해석된다.

STM Tip Catalyzed Adsorption of Thiol Molecules and Functional Group-Selective Adsorption of a Bi-Functional Molecule Using This Catalysis

  • 민영환;정순정;윤영상;박은희;김도환;김세훈
    • 한국진공학회:학술대회논문집
    • /
    • 한국진공학회 2011년도 제41회 하계 정기 학술대회 초록집
    • /
    • pp.197-197
    • /
    • 2011
  • In this study, in contrast with cases in which Scanning Tunneling Microscopy (STM) tip-induced reactions were instigated by the tunneling electrons, the local electric field, or the mechanical force between a tip and a surface, we found that the tungsten oxide (WO3) covered tungsten (W) tip of a STM acted as a chemical catalyst for the S-H dissociative adsorption of phenylthiol and 1-octanethiol onto a Ge(100) surface. By varying the distance between the tip and the surface, the degree of the tip-catalyzed adsorption could be controlled. We have found that the thiol head-group is the critical functional group for this catalysis and the catalytic material is the WO3 layer of the tip. After removing the WO3 layer by field emission treatment, the catalytic activity of the tip has been lost. 3-mercapto isobutyric acid is a chiral bi-functional molecule which has two functional groups, carboxylic acid group and thiol group, at each end. 3-Mercapto Isobutyric Acid adsorbs at Ge(100) surface only through carboxylic acid group at room temperature and this adsorption was enhanced by the tunneling electrons between a STM tip and the surface. Using this enhancement, it is possible to make thiol group-terminated surface where we desire. On the other hand, surprisingly, the WO3 covered W tip of STM was found to act as a chemical catalyst to catalyze the adsorption of 3-mercapto isobutyric acid through thiol group at Ge(100) surface. Using this catalysis, it is possible to make carboxylic acid group-terminated surface where we want. This functional group-selective adsorption of bi-functional molecule using the catalysis may be used in positive lithographic methods to produce semiconductor substrate which is terminated by desired functional groups.

  • PDF

1,3-티아졸리딘 술폭시드의 입체구조에 관한 연구 (A Study on the Stereochemistry of 1,3-Thiazolidine)

  • 마혜덕;박신자;한호규
    • 대한화학회지
    • /
    • 제37권1호
    • /
    • pp.119-130
    • /
    • 1993
  • 한 분자 내에 3개의 chiral 중심이 있는 1,3-티아졸리딘 술록시드 1의 입체화학을 중수소치환반응 및 trapping 반응을 통해 밝혔다. 3-아세틸-1,3-티아졸리딘 5의 부분이성질체를 분리한 다음 6과 8을 각각 술록시드로 산화시켜 상응하는 $\alpha$-시스 10, $\alpha$-트랜스 11과 $\beta$ -시스 12, $\beta$ -트랜스이성체 13을 얻었다. 술폭시드 10은 중성 조건하의 환류하는 벤젠 또는 톨루엔 용액 중에서 열역학적으로 보다 안정한 13으로 이성질화하였다. 중수소치환반응에 의해서 술폭시드 13과 술폭시드 11의 2-메틸기의 수소원자는 중수소로 치환되었다. 술폭시드 10과 12로부터 sigmatropic 전위에 의해서 생성된 중간체 슬페닌산 25 및 26은 2-머캡토벤조티아졸(2-MBT)에 의하여 trap되어 디술피드 27 및 28로 전환되었으나 동일한 반응조건하에서 술폭시드 11 및 13은 환팽창 생성물 디히드로-1,4-티아진 29로 전환되었다. 산촉매 존재하에서 술폭시드 10, 11, 12는 술폭시드 13을 통해서 디히드로-1,4-티아진 29로 정량적으로 전환되었다. 술폭시드들의 이성질화 및 29의 생성메카니즘도 기술하였다.

  • PDF