KR102066464B1 - 알킨의 헤테로아렌과의 카르보닐화를 위한 마르코브니코프-선택적 팔라듐 촉매 - Google Patents

알킨의 헤테로아렌과의 카르보닐화를 위한 마르코브니코프-선택적 팔라듐 촉매 Download PDF

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KR102066464B1
KR102066464B1 KR1020180074423A KR20180074423A KR102066464B1 KR 102066464 B1 KR102066464 B1 KR 102066464B1 KR 1020180074423 A KR1020180074423 A KR 1020180074423A KR 20180074423 A KR20180074423 A KR 20180074423A KR 102066464 B1 KR102066464 B1 KR 102066464B1
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carbonylation
markovnikov
palladium catalyst
heteroarenes
alkynes
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하오취안 리
제 리우
랄프 작스텔
마티아스 벨러
로베르트 프란케
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에보니크 오퍼레이션즈 게엠베하
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Abstract

알킨의 헤테로아렌과의 카르보닐화를 위한 마르코브니코프-선택적 팔라듐 촉매.

Description

알킨의 헤테로아렌과의 카르보닐화를 위한 마르코브니코프-선택적 팔라듐 촉매 {Markovnikov-selective palladium catalyst for carbonylation of alkynes with heteroarenes}
본 발명은 알킨의 헤테로아렌과의 카르보닐화를 위한 마르코브니코프-선택적 팔라듐 촉매에 관한 것이다.
리간드의 개발은 균일 촉매작용 및 유기 합성에서 주요 역할을 하며 유의한 혁신을 제공한다. 예시적인 예는 중합, 유기금속 커플링 반응, 카르보닐화, 수소화 및 복분해를 포함한다. 지난 수십 년간에 걸쳐 수많은 질소- 및 인-기재 리간드가 개발된 바 있지만, 용이하게 제조 및 개질 수 있는, 고도로 활성인 촉매 시스템을 제공하기 위한 이들의 합리적 설계는 계속해서 이러한 분야에서 중요한 주제이다.
공지된 특별한 리간드 부류 중에서도, 특히 이좌배위자 및 다좌배위자 유도체가 고도로 안정적이며 선택적인 유기금속 착물을 생성한다.
본 발명에 의해 해결하고자 하는 과제는 알킨의 카르보닐화를 위한 팔라듐 촉매의 리간드로서 우수한 특성을 가지며, 카르보닐화 반응의 수율과 관련하여 우수한 결과를 달성할 화합물을 제공하는 것이었다.
상기 과제는 청구범위의 제1항에 따른 화합물에 의해 해결된다.
구조 (1)을 갖는 화합물.
Figure 112018063447917-pat00001
추가적으로, 카르보닐화 반응의 촉매작용을 위한 리간드-금속 착물의 리간드로서의 상기 화합물의 용도가 청구된다.
카르보닐화 반응의 촉매작용을 위한 리간드-금속 착물에서의 상기 기재된 화합물의 용도.
상기 화합물이 올레핀의 알데히드로의 전환을 위한 리간드-금속 착물의 리간드로서 사용되는 방법도 마찬가지로 청구된다.
하기 방법 단계를 포함하는 방법:
a) 초기에 알킨을 충전하는 단계,
b) 상기 기재된 화합물 및 Pd를 포함하는 물질을 첨가하는 단계,
c) N-메틸피롤 및 CO를 공급하는 단계,
d) 반응 혼합물을 가열하면서, 알킨을 생성물로 전환시키는 단계.
이러한 방법에서, 방법 단계 a) 내지 d)는 임의의 목적하는 순서로 실시될 수 있다.
상기 방법의 바람직한 변형법에서, 금속 원자는 Rh이다.
본 발명은 작업 실시예에 의해 하기에서 상세히 설명된다.
리간드 합성
Figure 112018063447917-pat00002
N,N'-디피롤릴메탄의 합성
피롤 (9.00 ml, 130 mmol)을 실온에서 DMSO (100 ml) 중의 분말화된 수산화칼륨 (24 g, 0.43 mol, 3.31 당량)의 교반된 현탁액에 첨가하였다. 1시간 후에, 혼합물을 40℃로 가열하고, DCM (6.32 ml, 98.6 mmol, 0.76 당량)을 서서히 첨가하였다. 용액을 추가로 4시간 동안 40℃에서 가열하였다. 냉각되면, 에테르 (100 ml) 및 물 (100 ml)을 첨가하고, 층을 분리하였다. 수성 층을 에테르로 3회 추출하고, 합한 유기 추출물을 물로 3회, 이어서 염수로 세척하고, MgSO4로 건조시키고, 감압 하에 용매를 제거하여 연황색 고체를 제공하였다. 클로로포름으로부터의 재결정화에 의해 1,2-디(피롤-1-일)메탄을 72%의 수율로 제공하였다.
N, N'-디이미다졸메탄의 합성
N,N'-디피롤릴메탄과 유사
(1) 및 (2)의 합성:
100 ml 용량의 3구 둥근 바닥 플라스크에서, N, N'-디피롤릴메탄 (5 mmol)을 아르곤 하에 15 ml의 새로 증류된 Et2O에 용해시켰다. 실온에서 TMEDA (15 mmol), 이어서 n-BuLi (헥산 중 10.5 mmol, 1.6 M)를 첨가하였다. 반응 혼합물을 실온에서 1시간 동안 교반하여, 황색 현탁액을 수득하였다. 이어서, 황색 현탁액을 서서히 시린지를 통해 ClPR2의 용액 (15 ml Et2O 중 10 mmol, R = Ph 또는 Cy)에 첨가하였다. 혼합물을 추가로 1시간 동안 교반한 다음, 탈기수 (10 ml)를 첨가하고, 혼합물을 교반하여 투명한 용액을 얻었다. 수성 층을 Et2O (2x 15 ml)로 추출하고, 합한 유기 층을 탈기수 (10 ml)로 세척하였다. 용액을 Na2SO4 상에서 건조시키고, 농축시켜 황색 점성 액체를 얻었고, 이를 에탄올로부터 재결정화하였다. 수율 및 특징화에 대해서는 하기를 참조한다.
특징화:
Figure 112018063447917-pat00003
1.0 g, 39% 수율 (5 mmol 규모, 97% 순도), 백색 고체.
1H NMR (300 MHz, CD2Cl2) δ 7.23-7.18 (m, 20H), 6.85-6.83 (m, 2H), 6.17 (t, J = 2.8 Hz, 2H), 6.00 (dd, J = 3.6, 2.8 Hz, 2H), 5.83 (dd, J = 3.6, 1.6 Hz, 2H);
13C NMR (75 MHz, CD2Cl2) δ 137.1, 133.7, 129.1, 128.9, 127.8, 125.7, 119.8, 110.5, 58.1
31P NMR (122 MHz, CD2Cl2) δ -33.0.
HRMS (ESI) [C33H52N2P2+H]+ 계산된 질량 539.36785, 측정된 질량 539.36811.
Figure 112018063447917-pat00004
0.54 g, 20% 수율 (5 mmol 규모, 95% 순도), 회백색 고체.
1H NMR (300 MHz, d8-톨루엔) δ 7.18-7.15 (m, 2H), 6.53-6.51 (m, 2H), 6.40-6.38 (m, 2H), 6.31-6.29 (m, 2H), 1.86-1.56 (m, 24H), 1.25-1.06 (m, 20 H);
13C NMR (75 MHz, d8-톨루엔) δ 126.1, 124.3, 116.7, 109.6, 57.0, 34.2, 30.4, 29.1, 27.1;
31P NMR (122 MHz, d8-톨루엔) δ -31.0.
HRMS (ESI) [C33H52N2P2+H]+ 계산된 질량 539.36785, 측정된 질량 539.36811.
(3)의 합성:
Figure 112018063447917-pat00005
(1) 및 (2)와 유사
촉매 실험
Figure 112018063447917-pat00006
촉매 결과
촉매 실험의 결과가 표 1에 요약되어 있다:
표 1:
Figure 112018063447917-pat00007
* 본 발명의 화합물
알킨 = 1-옥틴
반응 조건: (Ia) (1.0 mmol), (IIa) (0.5 mmol), Pd(acac)2 (2.0 mol%), 리간드 (4.0 mol%), p-TsOH (10.0 mol%), CO (40 bar), 톨루엔 (1.0 mL), 70℃, 12시간.
상이한 알킨 (I)을 사용한 카르보닐화 실험의 추가의 결과가 표 2에 요약되어 있다:
표 2:
Figure 112018063447917-pat00008
반응 조건: 알킨 (I) (1.0 mmol), N-메틸피롤 (II) (0.5 mmol), Pd(acac)2 (1.0 mol%), (1) (2.0 mol%), p-TsOH (5.0 mol%), CO (40 bar), 톨루엔 (1.0 mL), 70℃, 12시간.
각 경우에, 단리된 화합물 (III)의 수율이 주어지며, 괄호 안의 숫자는 GC 분석에 의해 결정된 (III/III') 비를 나타낸다.
[a] 90℃에서의 반응.
[b] 20시간 동안 100℃에서의 반응.
[c] 20시간 동안 90℃에서의 반응.
상기 기재된 실험에 근거하여, 언급된 과제가 본 발명의 화합물에 의해 해결된 것으로 제시되었다.

Claims (3)

  1. 구조 (1)을 갖는 화합물.
    Figure 112018063447917-pat00009
  2. 카르보닐화 반응을 촉매하기 위해 제1항에 따른 화합물을 사용하는 방법.
  3. 하기 방법 단계를 포함하는 방법:
    a) 초기에 알킨을 충전하는 단계,
    b) 제1항에 따른 화합물 및 Pd를 포함하는 물질을 첨가하는 단계,
    c) N-메틸피롤 및 CO를 공급하는 단계,
    d) 반응 혼합물을 가열하면서, 알킨을 생성물로 전환시키는 단계.
KR1020180074423A 2017-06-29 2018-06-28 알킨의 헤테로아렌과의 카르보닐화를 위한 마르코브니코프-선택적 팔라듐 촉매 KR102066464B1 (ko)

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EP17178595.9 2017-06-29
EP17178595.9A EP3421478B1 (en) 2017-06-29 2017-06-29 Markovnikov-selective palladium catalyst for carbonylation of alkynes with heteroarenes

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