公开(公告)号：KR100821936B1

公开(公告)日：2008-04-15

申请号：KR1020060130535

申请日：2006-12-20

Applicant: 강원대학교산학협력단

Inventor： 이필호 ,  이구연 ,  서문동 ,  김현석

IPC: C07C13/11 ,  C07C13/00 ,  C07D209/10 ,  C07D267/04

CPC classification number: C07C67/317 ,  C07C1/325 ,  C07C13/465 ,  C07C67/327 ,  C07C253/30 ,  C07C315/04 ,  C07C2601/08 ,  C07C2602/08 ,  C07C2602/10 ,  C07C2603/24 ,  C07D209/08 ,  C07D267/04 ,  C07D267/22 ,  C07C69/74 ,  C07C69/753 ,  C07C69/757 ,  C07C317/12 ,  C07C317/44 ,  C07C255/47

Abstract: A method for coupling carbon atoms in an unsaturated hydrocarbon compound molecule by using organoindium is provided to avoid an additional purification step for separating an intermediate compound produced by a transition metal catalyst and indium, to solve the problem related with toxicity of an organotin compound, and to obtain a cyclic compound at a high yield. A method for coupling carbon atoms in an unsaturated hydrocarbon compound molecule comprises a step of carrying out in-situ reaction of an allyl substituent of the following formula 3 or 4 containing an unsaturated hydrocarbon compound with indium halide and a tertiary amine represented by the formula of NR2R3R4, in the presence of a palladium catalyst to form an allyl indium compound in which Z of the allyl substituent of formula 3 or 4 is substituted with indium, thereby providing a cyclic compound having a vinyl substituent represented by the following formula 1 or formula 2 through an in-situ intramolecular cyclization reaction. In the above formulae, X is Cl, Br or I; Y is (CH2)pCR11R12, NR13 or (CH2)qONR14; Z is Cl, Br, I, OAc or OCO2CH3; each of A, B, C and D independently represents H, a C1-C5 alkyl, phenyl or benzyl, or A and B or C and D are linked to each other via a C2-C10 alkylene, C2-C5 alkenylene, fused ring-containing C2-C10 alkylene or fused ring-containing C2-C5 alkenylene to form a ring optionally further comprising at least one heteroatom selected from N, O and S; R1 represents H, fluorine-substituted or non-substituted C1-C5 alkyl, C1-C5 alkoxy, C1-C5 alkoxycarbonyl or C1-C5 alkoxycarbonyl; each of R2, R3 and R4 represents a C1-C5 alkyl, phenyl or benzyl; each of R11 and R12 represents H, a C1-C5 alkyl, C1-C5 alkoxy, C1-C5 alkylcarbonyl or C1-C5 alkoxycarbonyl; R13 is a C1-C5 alkyl or SO2R21; R14 is t-butoxycarbonyl or a C1-C5 alkyl; R21 is a C1-C5 alkyl or phenyl; n is an integer of 1-4; m is an integer of 1-3; p is an integer of 0-5; and q is an integer of 1-3.

Abstract translation: 提供了通过使用有机铟偶联不饱和烃化合物分子中的碳原子的方法，以避免用于分离由过渡金属催化剂和铟生成的中间体化合物的另外的纯化步骤，以解决与有机锡化合物的毒性有关的问题，以及 以高收率得到环状化合物。 用于偶联不饱和烃化合物分子中的碳原子的方法包括以下步骤：将含有不饱和烃化合物的下式3或4的烯丙基取代基与卤化铟和由式 NR2R3R4，在钯催化剂存在下，形成烯键式铟化合物，其中式3或4的烯丙基取代基的Z被铟取代，从而提供具有由下式1或式2表示的乙烯基取代基的环状化合物 通过原位分子内环化反应。 在上式中，X是Cl，Br或I; Y是（CH 2）pCR 11 R 12，NR 13或（CH 2）qONR 14; Z是Cl，Br，I，OAc或OCO 2 CH 3; A，B，C和D各自独立地表示H，C1-C5烷基，苯基或苄基，或A和B或C和D通过C 2 -C 10亚烷基，C 2 -C 5亚烯基，稠环彼此连接 含有C 2 -C 10亚烷基或稠环的C 2 -C 5亚烯基以形成任选地进一步包含至少一个选自N，O和S的杂原子的环; R 1表示H，氟取代或未取代的C 1 -C 5烷基，C 1 -C 5烷氧基，C 1 -C 5烷氧基羰基或C 1 -C 5烷氧基羰基; R2，R3和R4各自表示C1-C5烷基，苯基或苄基; R11和R12各自表示H，C1-C5烷基，C1-C5烷氧基，C1-C5烷基羰基或C1-C5烷氧基羰基; R13是C1-C5烷基或SO2R21; R14是叔丁氧基羰基或C1-C5烷基; R 21是C 1 -C 5烷基或苯基; n为1-4的整数; m为1-3的整数; p是0-5的整数; q为1-3的整数。

公开(公告)号：KR101014885B1

公开(公告)日：2011-02-15

申请号：KR1020080066689

申请日：2008-07-09

Applicant: 강원대학교산학협력단

Inventor： 이필호 ,  서문동 ,  박용광

IPC: C07C2/64 ,  C07C15/44 ,  C07D213/00

CPC classification number: Y02P20/52

Abstract: 본 발명은 알릴 유도체와 인듐으로부터 제조되는 알릴 인듐 화합물과 아릴 브로마이드 또는 트리플루오로메탄술포네이트와의 교차-짝지음 반응을 통해서 효과적으로 하기 화학식 1로 표시되는 알릴벤젠 유도체를 제조하는 방법에 관한 것이다.

상기 화학식 1에서, A는 CR
4 또는 N을 나타내며; R
1 , R
2 , R
3 , R
4 또는 R
5 는 서로 독립적으로 수소, C
1 -C
5 의 알킬, C
1 -C
5 의 알콕시, C
1 -C
5 의 알킬카르보닐, C
1 -C
5 의 알콕시카르보닐, C
1 -C
5 의 아마이드, 벤질 아마이드 또는 니트릴을 나타내거나, R
1 과 R
2 또는 R
2 와 R
3 가 서로 연결되어 벤젠고리를 형성할 수 있으며; R
6 , R
7 또는 R
8 은 서로 독립적으로 수소, C
1 -C
5 의 알킬기 또는 C
1 -C
5 의 알콕시기를 나타낸다.
알릴 치환체, 알릴인듐, 교차-짝지움 반응, 인듐

公开(公告)号：KR100973580B1

公开(公告)日：2010-08-02

申请号：KR1020080056826

申请日：2008-06-17

Applicant: 강원대학교산학협력단

Inventor： 이필호 ,  김진호 ,  서문동

IPC: C07D307/36 ,  C07D307/34

Abstract: 본 발명은 퓨란 유도체와 금 및 은 촉매를 이용한 이의 제조방법에 관한 것으로, 보다 상세하게는 인아인-1,6-다이올 유도체를 금(Au) 및 은(Ag) 촉매 조건에서 산소-탄소간의 선택적인 분자내 고리화 반응을 수행하여 제조된 신규 구조의 하기 화학식 1로 표시되는 퓨란 유도체와 이의 제조방법에 관한 것이다.

상기 화학식 1에서, A는 C
1 -C
6 알킬기; C
5 -C
8 사이클로알킬기; 또는 할로겐, 하이드록실, C
1 -C
4 알킬, C
1 -C
4 알콕시, C
2 -C
4 알카노에이트 중에서 선택된 치환체가 하나 이상 치환 또는 비치환된 페닐기를 나타낸다.
금촉매, 은촉매, 인아인-1,6-다이올, 분자내 고리화반응, 퓨란

公开(公告)号：KR1020100006456A

公开(公告)日：2010-01-19

申请号：KR1020080066689

申请日：2008-07-09

Applicant: 강원대학교산학협력단

Inventor： 이필호 ,  서문동 ,  박용광

IPC: C07C2/64 ,  C07C15/44 ,  C07D213/00

CPC classification number: Y02P20/52

Abstract: PURPOSE: A method for manufacturing allyl benzene derivatives is provided to be applied in the synthesis of various natural products, to prepare allyl benzene derivatives at high yield compared with a conventional allyl indium reaction, and to compensate toxicity of organic tin compound. CONSTITUTION: A method for manufacturing allyl benzene derivatives comprises the steps of: reacting an allyl derivative represented by chemical formula 2, indium halide represented by chemical formula 3, amine compound represented by chemical formula 4, in the indium, palladium catalyst, and ligand condition to prepare allyl indium represented by chemical formula 5; performing cross coupling reaction of the allyl indium with an allyl compound represented by chemical formula 6 to prepare an allyl benzene derivative represented by chemical formula 1.

Abstract translation: 目的：提供一种制备烯丙基苯衍生物的方法，用于合成各种天然产物，与常规的烯丙基铟反应相比，以高产率制备烯丙基苯衍生物，并补偿有机锡化合物的毒性。 构成：制造烯丙基苯衍生物的方法包括以下步骤：使由化学式2表示的烯丙基衍生物，由化学式3表示的卤化铟，由化学式4表示的胺化合物反应在铟，钯催化剂和配体条件 制备由化学式5表示的烯丙基铟; 进行烯丙基铟与化学式6表示的烯丙基化合物的交叉偶联反应，制备由化学式1表示的烯丙基苯衍生物。

公开(公告)号：KR1020090131051A

公开(公告)日：2009-12-28

申请号：KR1020080056826

申请日：2008-06-17

Applicant: 강원대학교산학협력단

Inventor： 이필호 ,  김진호 ,  서문동

IPC: C07D307/36 ,  C07D307/34

Abstract: PURPOSE: A method for preparing a novel furan derivative, gold and silver catalyst is provided to used as an intermediate when synthesizing medicinal and pharmaceutical product or perfume. CONSTITUTION: A furan derivative is denoted by chemical formula 1. In chemical formula 1, A is alkyl group of C1-C6, cylcoalkyl group of C5-C8, or halogen, hydroxyl, alkyl of C1-C4, alkoxy of C1-C4 or alkanoate substitute of C2-C4 or unsubstituted phenyl group. The furan derivative is obtained by reacting cyclization of enyne-1,6-diol derivative of chemical formula 2 under the presence of gold(Au) and silver(Ag) catalyst. The gold(Au) catalyst is Au^+ or Au^3+ ion-containing compound. The silver(Ag) catalyst is Ag^+ ion-containing compound.

Abstract translation: 目的：提供一种制备新型呋喃衍生物，金和银催化剂的方法，用作合成药物和药物或香料时的中间体。 构成：呋喃衍生物由化学式1表示。在化学式1中，A为C 1 -C 6烷基，C 5 -C 8环烷基或卤素，羟基，C 1 -C 4烷基，C 1 -C 4烷氧基或 C2-C4或未取代苯基的链烷酸酯替代物。 通过在金（Au）和银（Ag）催化剂的存在下使化学式2的烯-1,6-二醇衍生物环化反应获得呋喃衍生物。 金（Au）催化剂是含Au +或Au ^ 3 +离子的化合物。 银（Ag）催化剂是含Ag +离子的化合物。