有機(jī)聚合物負(fù)載的手性催化劑研究與進(jìn)展

徐圓圓, 程探宇, 魏 星, 李曉敏, 陳倩蕓, 劉國(guó)華

(上海師范大學(xué) 生命與環(huán)境科學(xué)學(xué)院,上海 200234)

0 引 言

半個(gè)世紀(jì)之前Merrifield第一次報(bào)道了通過(guò)用聚苯乙烯為載體固相合成多肽鏈[1],自此之后以聚合物為載體被廣泛的應(yīng)用于簡(jiǎn)易合成、產(chǎn)物提純等領(lǐng)域.類似于Merrifield樹(shù)脂這種非均相的聚苯乙烯仍然應(yīng)用于各種固相合成,還應(yīng)用于各種反應(yīng)試劑或催化劑的固載方面,而且越來(lái)越多的大分子材料應(yīng)用于這些領(lǐng)域.Hudson將在1999年之前使用聚合物固載的主要研究者的工作做了非常全面的綜述[2,3],另外包括聚乙二醇、非交聯(lián)聚苯乙烯、聚乙烯、聚丙酸等一些可溶性的聚合物的應(yīng)用也有較多的綜述文獻(xiàn)[4-7].近年來(lái),隨著醫(yī)藥合成領(lǐng)域的快速發(fā)展,手性催化劑也隨之發(fā)展迅速,而聚合物應(yīng)用與手性催化劑的固載也越來(lái)越多.本文作者主要綜述了有機(jī)聚合物固載型手性催化劑的研究進(jìn)展.

1 聚合物負(fù)載的有機(jī)小分子手性催化劑

早在20世紀(jì)化學(xué)家就發(fā)現(xiàn)了生物堿[8]和L-脯氨酸[9]的不對(duì)稱催化作用.隨后的幾十年間手性小分子催化劑引起了廣大的關(guān)注,并且發(fā)展迅速.近年來(lái)有機(jī)小分子手性催化劑越來(lái)越多的被負(fù)載在聚合物上,使之能夠降低催化劑成本、更加利于回收.以近年來(lái)應(yīng)用較為廣泛的金雞納堿、咪唑啉酮和脯氨酸為例,介紹聚合物負(fù)載的有機(jī)小分子手性催化劑.

1.1 金雞納堿

2008年Itsuno等報(bào)道了一種新穎的固載季銨鹽手性催化劑的方法,他們將聚合物鏈上引入磺酸根負(fù)離子,然后與季銨鹽催化劑以離子鍵相結(jié)合形成聚合物負(fù)載的金雞納堿類似物催化劑1[10](圖1).該催化劑可以催化N-(二苯基亞甲基)氨基乙酸叔丁酯和芐溴(或烯丙基溴)反應(yīng),收率高達(dá)95%(91% 對(duì)映體過(guò)量),但是該催化劑對(duì)碘甲烷反應(yīng)活性不高,收率45%(70% 對(duì)映體過(guò)量ee).作者推測(cè)催化劑在催化過(guò)程中,離子蔟起了較為重要的作用.它促使了底物的烯醇化,并且活化了芐溴,反應(yīng)后釋放出催化劑并得到手性產(chǎn)物.

圖1 負(fù)載型金雞納堿催化劑

隨后Itsuno等又報(bào)道了金雞納堿季銨鹽與二磺酸根負(fù)離子形成的高聚物催化劑2[11-12](圖2),在室溫條件下、堿性環(huán)境中,加入催化劑2(10 mol%)可以使N-(二苯基亞甲基)氨基乙酸叔丁酯不對(duì)稱烷基化,而且收率和ee值都比較理想.作者認(rèn)為該催化劑可以拓展為一種平臺(tái),適用于各種以離子鍵相結(jié)合的催化劑.

Haraguchi在2012年報(bào)道了與Itsuno相似的高聚物催化劑3[13](圖2),作者以金雞納堿季銨鹽為催化單體,用二鹵素有機(jī)物通過(guò)共價(jià)鍵將金雞納堿相連形成高聚物催化劑.金雞納堿的二聚體催化N-(二苯基亞甲基)氨基乙酸叔丁酯不對(duì)稱烷基化時(shí)可以得到較好的收率(>90%)和ee值(>80%).但是當(dāng)二聚體再次以二鹵素化合物相連形成高聚物催化劑后,其催化效率有所下降,其中收率和ee值都下降了約10%(圖2).

圖2 自聚型金雞納堿催化劑

1.2 咪唑啉酮

早在2002年,Cozzi[8]等就將咪唑啉酮的酪氨酸衍生物固載在可溶性的聚乙二醇上,用于催化Diels-Alder反應(yīng).該催化劑對(duì)映選擇性較好(92% ee),另外它還可以重復(fù)使用4次,但是催化效率和對(duì)映選擇性都有所降低.在2004年Benaglia和Cozzi同樣將咪唑啉酮的衍生物固載在聚乙二醇上得到催化劑4[14](圖3),它可用于催化N-芐基苯硝酮和丙烯醛在酸性條件下的Diels-Alder反應(yīng).負(fù)載催化劑4與負(fù)載前催化劑對(duì)映選擇性沒(méi)有區(qū)別,但是催化效率有所降低,另外該催化劑可以方便的回收利用3次.

Haraguchi等將咪唑啉酮衍生得到其季銨鹽,然后通過(guò)離子鍵負(fù)載在有磺酸根負(fù)離子功能化的交聯(lián)聚苯乙烯上得到催化劑5[9](圖3).該催化劑可以催化環(huán)戊二烯和肉桂醛的環(huán)加成反應(yīng),得到較好的對(duì)映選擇性(91% ee),而且它的重復(fù)使用無(wú)需經(jīng)過(guò)重生步驟.Pericàs等通過(guò)Click反應(yīng)將咪唑啉酮的衍生物固載與聚苯乙烯上得到催化劑6[15](圖3),其可在0.5 mol/L的三氟乙酸的THF體系中催化氮取代的吡咯進(jìn)行烷基化.該催化劑重復(fù)使用6次而其對(duì)映選擇性基本沒(méi)有變化,但是催化效率有所降低(圖3).

圖3 負(fù)載型咪唑啉酮催化劑

1.3 脯氨酸

L-脯氨酸及其衍生物是一類最簡(jiǎn)單有效的有機(jī)小分子催化劑,它可以催化aldol反應(yīng)[16]、Robinson縮環(huán)反應(yīng)[17]、Mannich反應(yīng)[18]、Michael反應(yīng)[19]、Diels-Alder反應(yīng)[20]和一些其他反應(yīng)[21-26].(2S,4R)-4-羥基脯氨酸被固載在PEG500上形成可溶性的催化劑7(圖4),它可以用于催化aldol縮合和Mannich反應(yīng)[27,28],而且脯氨酸固載前后的催化效率和對(duì)映選擇性沒(méi)有明顯變化.用于硝基苯甲醛和丙酮的縮合反應(yīng),催化劑7重復(fù)使用3次而ee值沒(méi)有變化,但是收率有比較明顯的降低(68%～51%).另外該催化劑還可以用于催化2-硝基丙烷和環(huán)己烯酮的加成反應(yīng)[29],而用于β-硝基苯乙烯與酮的加成時(shí)對(duì)映選擇性(40% ee)比均相脯氨酸(60% ee)低.

圖4 負(fù)載型脯氨酸催化劑

Zhao等報(bào)道了與7相似的催化劑8～10[29],研究發(fā)現(xiàn)對(duì)于環(huán)己酮與β-硝基苯乙烯的反應(yīng),催化劑10無(wú)論是效率還是對(duì)映選擇性都比8和9要好.催化劑可以通過(guò)加入非極性溶劑析出,過(guò)濾回收后可再次使用四次,但是收率(92-24%)和對(duì)映選擇性(60-<10%)都有非常明顯的降低.

除了將脯氨酸固載在可溶性的聚乙二醇上,不溶性的聚苯乙烯類樹(shù)脂也作為一類載體被廣泛的使用.各種脯氨酸的衍生物通過(guò)Click反應(yīng)固載在樹(shù)脂上,用于aldol反應(yīng)[30-31]、α-胺氧化反應(yīng)[32]、Michael加成反應(yīng)[33]、α-硒化反應(yīng)[34]等.

2 聚合物負(fù)載的手性有機(jī)金屬催化劑

手性金屬絡(luò)合物催化劑在不對(duì)稱催化中始終扮演著及其重要的角色,2001年度的諾貝爾化學(xué)獎(jiǎng)就授予了從事手性催化的Knowles、Noyori和Sharpless 3位化學(xué)家.但是隨著工業(yè)的發(fā)展,由于手性金屬絡(luò)合物催化劑尤其是重金屬催化劑容易造成的環(huán)境污染,而且他們的成本一般相對(duì)較高,這些原因大大的限制了其發(fā)展.而近年來(lái)手性催化劑的固載技術(shù)緩解了這些問(wèn)題,而且越來(lái)越多的手性催化劑被固載與有機(jī)聚合物和介孔硅膠材料上.本文作者以固載與有機(jī)聚合物上的鈷、釕和銠等重金屬催化劑為例介紹近年來(lái)有機(jī)聚合物負(fù)載金屬手性催化劑的發(fā)展情況.

2.1 鈷

圖5 負(fù)載型手性鈷催化劑

Jacobsen等在1999年將手性的Co(Salen)固載與聚苯乙烯上得到催化劑11[35](圖5),該催化劑可以在二氯甲烷中水解端基的環(huán)氧乙烷得到手性(>92% ee)的二醇化合物,另外它可以重復(fù)使用5次.幾年后Jones和Weck以大環(huán)相連的低聚物12[36](圖5),催化單元同樣為手性鈷催化劑,該催化劑是通過(guò)烯烴的擴(kuò)環(huán)得到.在有氧的酸性條件下,12可以水解單一構(gòu)型的端基環(huán)氧乙烷,得到手性的環(huán)氧乙烷和手性的二醇化合物,而且該催化劑的催化活性(收率>42%)和對(duì)應(yīng)選擇性(>98% 對(duì)映體過(guò)量值)都非常好.值得一提的是這種以大環(huán)相連的低聚物比以烯烴鏈直接聚合得到的催化劑催化活性高很多.

2.2 釕

金屬釕是一種非常重要的過(guò)渡金屬元素,它可以催化較多種類的反應(yīng).而很多該類催化劑都被負(fù)載在無(wú)機(jī)介孔硅膠材料[37-41]和聚合物材料[42-48]上.在此簡(jiǎn)單介紹幾個(gè)比較有代表性的手性釕催化劑.催化劑13[45](圖6)是以聚苯乙烯樹(shù)脂為載體、吡啶雙噁唑啉為手性配體與金屬釕配位形成的手性負(fù)載型催化劑.該催化劑可以有效的催化苯乙烯和重氮乙酸乙酯的環(huán)丙化,得到主要為反式的環(huán)丙烷產(chǎn)物,ee值高達(dá)85%,但是13的催化劑效率較低(收率<40%).Haraguchi課題組在2009年報(bào)道了以TsDPEN為手性配體的催化劑14[43](圖6),他們選擇兩類聚苯乙烯載體,分別為疏水性的交聯(lián)聚苯乙烯和兩親性的交聯(lián)聚苯乙烯.疏水性的催化劑在有機(jī)溶劑(如二氯甲烷、乙腈)可以有效的催化亞胺的氫轉(zhuǎn)移得到手性的仲胺,在水環(huán)境中催化效率較差.而兩親性的催化劑在水環(huán)境中的催化效率較高,但是在有機(jī)環(huán)境中基本沒(méi)有催化活性.催化劑15[42](圖6)同樣為聚苯乙烯為載體的手性催化劑,它和13類似催化苯乙烯和重氮乙酸乙酯的環(huán)丙化反應(yīng),而且該催化劑反應(yīng)活性和對(duì)映選擇性都非常好(收率>90%,>90% ee).

2.3 銠

圖6 負(fù)載型金屬釕催化劑

圖7 自組裝型金屬銠催化劑

2.4 其他金屬

除了以上介紹的常被用于有機(jī)聚合物金屬非均相催化劑外,還要一些金屬也被化學(xué)家們用于有機(jī)聚合物的非均相催化.例如銅離子,手性的噁唑啉配體可以聚合成高聚物形成非均相催化劑[55],或者通過(guò)多個(gè)噁唑啉配體與銅離子配位相連形成類似于MOF的材料[56].這兩種催化劑都可以催化苯乙烯和重氮乙酸乙酯的環(huán)丙化,但是回收再利用比較差.還有Pd[57-58]和Mo[59-61]都曾被用于有機(jī)聚合物非均相催化劑,但是結(jié)果比均相的催化劑活性或?qū)τ尺x擇性差.

3 展 望

手性催化劑目前正在高速發(fā)展的階段,但是由于成本、環(huán)境等問(wèn)題大大的限制了其實(shí)際應(yīng)用.而非均相催化劑在一定程度上可以克制以上缺點(diǎn),使手性催化劑慢慢走向工業(yè)化.而有機(jī)聚合物制備簡(jiǎn)單、廉價(jià)易得,另外有機(jī)聚合物種類繁多,具有各種各樣的形狀,所以有機(jī)聚合物非均相手性催化劑具有較好的前景.但是目前其還在起步階段,存在一些缺點(diǎn),例如回收再利用次數(shù)不如無(wú)機(jī)介孔負(fù)載的手性催化劑多,還有就是聚合物使用單一(多為聚苯乙烯).相信在化學(xué)家們的不懈努力下,其一定會(huì)走向?qū)嶋H應(yīng)用、走向工業(yè)化.

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