기능화 인돌, 카바졸, 바이남의 새로운 합성 방법

Abstract

유기화학 합성과 산업 분야에서 N-aryl hydrazides는 hetrocyclic 또는 biaryl compounds 합성에 유용한starting material이다. Cu 또는 Pd 촉매 조건 하에서 alkyl carbazates와 substituted aryl halides 또는 trifuoromethane-sulfonate를 coupling하여 다양한 N-aryl hydrazides를 합성할 수 있다. 이렇게 합성한 N-aryl hydrazides로부터 새로운 합성 방법을 개발하여 다양한 기능성 유기 물질 carbazoles, indoles, 그리고 BINAMs를 합성할 수 있었다. Mono-N-Boc-diaryl hydrazides와 2,2′-diamino-1,1′-biaryls로부터 새로운 합성 방법 acid-catalyzed ring closing condensation를 이용하여 다양한 benzo[c]carbazoles 유도체를 좋은 수율로 효율적으로 합성할 수 있었다. Fischer indole synthesis의 선택적으로 indole를 합성할 수 없다는 문제점을 enotriflates와 aryl hydrazides로부터 합성한 ene-hydrazide를 가지고 the regioselective Fischer indolization하여 선택적으로indole을 좋은 수율과 비율로 합성하였다. 새로운 합성 방법은 기존 fischer indole synthesis로 합성하기 어려웠던 natural β-carboline alkaloid인 desbromoarborescidine A를 효율적으로 합성할 수 있었다. Aryl halides와 N-Boc hydrazine의 분자 간 C-N Cu-catalyzed coupling 반응은 쉽게 N-aryl hydrazide를 합성할 수 있지만 para, meta와 달리 ortho-substrated aryl hydrazide는 낮은 수율과 좋지 않은 선택성으로 합성하기 어려웠다. 새로운 분자 내 Cu-catalyzed coupling 반응은 이러한 문제점을 해결하고 좋은 수율로 ortho-substrated aryl hydrazides를 합성하였다. 나아가 합성한 aryl hydrazides로부터 낮은 온도에서 acid-catalyzed [3,3]-sigmatropic rearrangment를 이용하여 새로운 3,3′-disubstituted-2,2′-diamino- 1,1′-biaryl를 좋은 수율로 합성할 수 있었다. |Because of the usefulness to synthesize heteocyclic or biaryl compound, substituted N-aryl hydrazides are a valuable starting material in such field as organic synthesis and industry. Substituted aryl halides or trifuoromethanesulfonates are coupled with alkyl carbazates in the presence of a Cu/L or Pd/L-catalyst and base to afford N-aryl hydrazides. Functionalized organic materials such as carbazoles, indoles, and BINAMs are synthesized from N-aryl hydrazide and the study of new synthetic routes to functionalized organic materials is conducted. 2,2′-Diamino-1,1′-biaryls were found to undergo ring-closure condensation reaction to afford benzo[c]carbazoles in good to excellent yield. Coupled with the synthesis of 2,2′-biaryldiamines from diaryl hydrazides via [3,3]-sigmatropic rearrangement, it constitutes a new efficient synthetic method for benzo[c]carbazoles and related compounds. Ene-hydrazide prepared from enol triflate undergoes a Fischer indolization to give the corresponding indole with complete regioselectivity. This new protocol was successfully applied to the synthesis of desbromoarborescidine A, a natural β-carboline alkaloid, which is difficult to prepare with conventional Fischer indole synthesis. Previous synthetic method of aryl hydrazide which is conducted by intermolecular C-N Cu-catalyzed coupling of ortho-substituted aryl iodides with N-Boc hydrazine has issues such as resulting low yield and bad regioselectivity. This problem can be solved by intramolecular Cu-catalyzed coupling of ortho-O-substituted aryl iodides which is a new synthetic route. The ortho-O-substituted N-aryl hydrazide undergoes acid-catalyzed [3,3]-sigmatropic rearangement to afford 3,3′-disubstituted-2,2′-diamino- 1,1′-biaryl in good to excellent yield. The resultant products can be a versatile synthetic platforms for a wide variety of nonsymmetric axially chiral ligands and organocatalysts.; Because of the usefulness to synthesize heteocyclic or biaryl compound, substituted N-aryl hydrazides are a valuable starting material in such field as organic synthesis and industry. Substituted aryl halides or trifuoromethanesulfonates are coupled with alkyl carbazates in the presence of a Cu/L or Pd/L-catalyst and base to afford N-aryl hydrazides. Functionalized organic materials such as carbazoles, indoles, and BINAMs are synthesized from N-aryl hydrazide and the study of new synthetic routes to functionalized organic materials is conducted. 2,2′-Diamino-1,1′-biaryls were found to undergo ring-closure condensation reaction to afford benzo[c]carbazoles in good to excellent yield. Coupled with the synthesis of 2,2′-biaryldiamines from diaryl hydrazides via [3,3]-sigmatropic rearrangement, it constitutes a new efficient synthetic method for benzo[c]carbazoles and related compounds. Ene-hydrazide prepared from enol triflate undergoes a Fischer indolization to give the corresponding indole with complete regioselectivity. This new protocol was successfully applied to the synthesis of desbromoarborescidine A, a natural β-carboline alkaloid, which is difficult to prepare with conventional Fischer indole synthesis. Previous synthetic method of aryl hydrazide which is conducted by intermolecular C-N Cu-catalyzed coupling of ortho-substituted aryl iodides with N-Boc hydrazine has issues such as resulting low yield and bad regioselectivity. This problem can be solved by intramolecular Cu-catalyzed coupling of ortho-O-substituted aryl iodides which is a new synthetic route. The ortho-O-substituted N-aryl hydrazide undergoes acid-catalyzed [3,3]-sigmatropic rearangement to afford 3,3′-disubstituted-2,2′-diamino- 1,1′-biaryl in good to excellent yield. The resultant products can be a versatile synthetic platforms for a wide variety of nonsymmetric axially chiral ligands and organocatalysts.