CN104327121B - 一种螺环单齿配合物及其制备方法与应用 - Google Patents
一种螺环单齿配合物及其制备方法与应用 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2291—Olefins
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D309/10—Oxygen atoms
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- C—CHEMISTRY; METALLURGY
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/48—Ring-opening reactions
- B01J2231/482—Ring-opening reactions asymmetric reactions, e.g. kinetic resolution of racemates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/64—Molybdenum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/66—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
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- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Color Printing (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了结构通式（I）所示的螺环单齿配合物，其中，R为卤素、硝基、1‑4个碳原子的烷基、1‑4个碳原子的烷氧基，R1是2,6‑二异丙基苯基或金刚烷基，M是Ru、Mo或W。该化合物可以催化烯烃的不对称开环/交叉复分解反应。
Description
技术领域
本发明涉及一类基于螺环结构的“stereogenic-at-metal”的配合物及其制备方法。
背景技术
烯烃复分解反应是形成C=C键强有力的方法之一，该反应不仅可以通过简单烯烃制备复杂烯烃；而且反应中几乎不产生副产物或只产生乙烯这种极易除去的副产物。自上世纪该反应被发现以来，对它的研究和开发倍受青睐，已经被广泛用于高分子材料及有机中间体的合成。由于该反应的特殊性，不可能存在“普适性”的催化剂，因而需要人们不断探讨适用于各种不同底物的催化剂。据发明人了解，已有报道的 “stereogenic-at-metal”单齿配体手性催化剂结构仅限于BINOL型或联苯型单齿配体催化剂。
发明内容
本发明的目的之一是提供一种螺环单齿stereogenic-at-metal配合物；
本发明的另一目的是提供上述配合物的制备方法；
本发明还有一个目的是提供上述配合物催化剂在不对称复分解反应中的应用。
本发明实现过程如下：
结构式（I）所示的化合物，
其中，R为卤素、硝基、1-4个碳原子的烷基、1-4个碳原子的烷氧基；
R1是2,6-二异丙基苯基或金刚烷基；
M是Ru、Mo或W。
上述化合物中螺二氢茚骨架可以是消旋体或单旋体。
结构式（I）化合物的制备方法如下，
在-50度下，将化合物B的***溶液滴加到化合物A***溶液中，缓慢升温至室温，反应颜色渐变为红色，减压除去溶剂，用正戊烷重结晶得到化合物C。
上述化合物可应用在烯烃不对称复分解反应中。
本发明的优点与积极效果：本发明结构中螺二氢茚结构是一类优秀的手性诱导源，它作为配体紧邻金属手性中心，对复分解反应产生很好的手性诱导作用。
具体实施方式
以下通过实施例对本发明做进一步说明。
实施例1 (S)-6,6'-二溴-螺二氢茚二酚的合成
氮气保护下，将0.252g(1mmol)螺环二酚与DIPA (0.1mL,0.5mmol)置于5 mL二氯甲烷中，在0℃下下搅拌，再将10mL浓度为0.1mol/L NBS/二氯甲烷溶液缓慢滴加到该体系中，持续搅拌6小时； TLC检测反应停止，用CH2Cl2萃取，有机层用无水硫酸镁干燥，石油醚：乙酸乙酯（V/V）=7:1条件下柱层析分离得到产品，熔点152-154℃表征与结构相符。H NMR（300，） δ 7.31（d，2H），6.74（d，2H），5.25（s，2H），2.95-3.06（m，4H），2.36-2.41（m，2H），2.21-2.27（m，2H）。
实施例2手性螺二氢茚衍生物的合成
氮气氛围下，将(S)-6,6'-二溴-螺二氢茚二酚（0.1g，0.19mmol）溶解在10mL二氯甲烷中，加入0.1mL三乙胺，在22℃下搅拌；快速加入0.2 mL TBSOTf，继续搅拌10min，用TLC检测反应结束，用CH2Cl2萃取，有机层用无水硫酸镁干燥，旋转蒸发除去溶剂，用石油醚：乙酸乙酯（v:v=10:1）柱层析得到纯品，熔点144-146℃。1HNMR（400Hz，DCl3） δ7.37（d，2H）6.68-6.77（d，2H），5.20（m，1H)，2.87-2.97（m，4H），2.23-2.26（m，2H），2.11-2.14（m，2H），0.81（s，9H），0.15（m，6H）。
实施例3
以R=Br，R1=2,6-i-Pr2C6H3为例，在手套箱中，-50度下，将150 mg A和4 mL***置于密封容器中搅拌，同时将盛有0.6 mL含有 133 mg B的***溶液的施耐克也在手套箱密封起来，冷却至-50度，此时将B用滴管加入到A溶液中，并再用0.6 mL***将B完全移入A容器中，混合液的体系继续搅拌，缓慢升温至室温，反应颜色渐变为红色，2小时后，体系减压除去溶剂，得到的残余物用5 mL正戊烷溶解，减压除去正戊烷，得到粉末状产物，再将此粉状固体溶解在2 mL正戊烷中并搅拌，待所有固体溶解后，体系封闭起来，置于-50度过夜，有大量针状红色晶体析出，收集起来得到产物C。
实施例4含有不同取代基的手性螺环单齿配体合成结果
实施例5 手性螺环单齿配体在不对称开环/交叉复分解反应中的应用
室温下，在手套箱中，将商品试剂A（10 mg, 16.9 μmol）和上述手性螺二氢茚衍生物B（8.82 mg, 16.9 μmol）和苯（845μL,0.02M）置于单口瓶中搅拌2小时，溶液颜色渐变为橘红色，得到产物C；再加入苯乙烯（0.42mL, 3.5mmol）持续搅拌5分钟后，加入桥环底物D（0.42g, 1.8mmol）的8mL苯溶液，保持其浓度为0.2M，持续搅拌1小时，停止反应，反应体系从手套箱中取出。浓缩去除溶剂，产物经柱层析得到淡黄色产品，产率65%。1HNMR（400Hz，DCl3）δ7.33-7.6（m，5H）,6.61（d，1H），5.80（d，1H)，5.25-5.7（m，3H），4.25-4,28（m，2H），3.21（s，3H），2.8（t，1H），1.5-1.7（m，4H）。
Claims (1)
1.结构通式（I）所示的化合物在不对称开环/交叉复分解反应中的应用，
其中，R为卤素、硝基、1-4个碳原子的烷基、1-4个碳原子的烷氧基；
R1是2,6-二异丙基苯基或金刚烷基；
M是Mo。
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| CN100410218C (zh) * | 2006-04-06 | 2008-08-13 | 武汉大学 | 1,1ˊ-螺二氢茚或其衍生物的制备方法 |
| JP6266509B2 (ja) * | 2011-06-03 | 2018-01-24 | マサチューセッツ インスティテュート オブ テクノロジー | Ｚ選択的閉環メタセシス反応 |
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