CN115707518A - 一种手性双核铑金属催化剂及其制备方法和应用 - Google Patents
一种手性双核铑金属催化剂及其制备方法和应用 Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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Abstract
Description
技术领域
本发明属于催化剂领域。更具体地,涉及一种手性双核铑金属催化剂及其制备方法和应用。
背景技术
手性是自然界的基本属性之ー。近年来,人们对单一手性化合物(如手性医药和农药等)及手性功能材料的需求推动了手性科学的蓬勃发展。手性物质的获得,除了来自天然以外,人工合成是主要的途径。外消旋体拆分、底物诱导的手性合成和手性催化合成是获得手性物质的三种方法。手性催化研究是目前化学学科最为活跃的研究领域之一。
手性双核铑金属催化剂在不对称催化、天然产物全合成、有机合成方法学等领域发挥了非常重要的作用。例如手性双核铑金属催化剂可分解重氮产生高活性的铑卡宾中间体,该中间体可进行各种不对称的卡宾转移反应,如环丙烷化,碳氢、硅氢和硼氢插入等反应,为含环丙烷骨架以及含硅、硼等手性分子的构建提供了方法。手性双核铑金属催化剂还可作为路易斯酸,通过与杂原子配位,进行不对称的杂狄尔斯-阿尔德反应。此外,手性双核铑金属催化剂还可作为亲π型的路易斯酸,用于活化炔烃,以炔烃作为前体产生卡宾,同样也可进行多种不对称卡宾转移反应。总的来说,手性双核铑金属催化剂可催化各种有机反应,为各类手性分子的构建提供了一条行之有效的策略。因此发展手性双核铑金属催化剂具有重要意义。
目前,手性双核铑金属催化剂的库还不够完善。以羧酸铑为例,从结构上看,它们都局限于羧基直接相连的碳是手性碳,通过该位点对底物产生手性诱导作用,以此控制产物的手性,而这往往对催化中心附近的手性中心的立体控制效果较好,对于远程的手性控制能力相对较弱。此外,现有的催化剂由于手性中心和羧基相连的碳碳单键容易发生旋转,大部分现有的催化剂均是通过大位阻取代基来实现好的手性诱导效果,通过增加配体结构刚性的策略目前还少有报道。
部分市售的手性双核铑金属催化剂结构式如下:
发明内容
本发明要解决的技术问题是克服现有技术的缺陷和不足,提供一种具有新型骨架的手性双核铑金属催化剂。该手性双核铑金属催化剂可用于催化不对称反应。
本发明另一目的是提供一种手性双核铑金属催化剂的制备方法。
本发明另一目的是提供一种手性双核铑金属催化剂的应用。
本发明上述目的通过以下技术方案实现:
一种手性双核铑金属催化剂,具有式(I)所示结构,
其中,R1选自氢、取代或未取代的C1~C6直链或支链烷基或取代或未取代的C6~14芳基;R2选自对甲苯磺酰基、叔丁氧基羰基、苯基或苄基。
所述取代的C1~C6直链或支链烷基任意一个或多个氢原子被羟基或被保护基保护的羟基取代。
所述取代的C6~14芳基上任意一个或多个氢原子被取代基取代,所述取代基选自卤素、C1~6直链或支链烷基或取代或未取代的苯基;所述取代的苯基上任意一个或多个氢原子被C1~C6直链或支链烷基、卤素或苯基取代。
优选地,R1选自氢、C1~C6直链或支链烷基或C6~10芳基。
更优选,R1选自氢、C1~C6直链或支链烷基或苯基。
优选地,上述羟基的保护基为叔丁基二甲基硅基。
优选地,R2选自对甲苯磺酰基。
本发明使用的术语“芳基”,表示含有6~14个成环碳原子或6~10个成环碳原子的单环、双环或三环的碳环体系。这样的实例包括,但并不限于,苯基、萘基、菲基或蒽基。
本发明使用的术语“烷基”,表示含有1~6个碳原子,饱和的直链或支链一价烃基基团。在实施方案中,烷基基团含有1~6个碳原子;在另一实施方案中,烷基基团含有1~3个碳原子。
术语“卤素”指氟、氯、溴、碘。
更优选地,所述手性双核铑金属催化剂的结构,如下结构式之一所示:
所述手性双核铑金属催化剂的制备方法也在本发明的保护范围内,包括如下步骤:
式(II)所示的环丙羧酸化合物在溶剂中与铑金属催化剂发生配体交换,得到式(I)所示的手性双核铑金属催化剂;
其中R1、R2如本发明所定义。
优选地,反应可以如下进行:式(II)所示的环丙羧酸化合物在溶剂中与铑金属催化剂发生配位反应,得到式(I)所示的手性双核铑金属催化剂;
优选地,手性双核铑金属催化剂的制备方法还包括如下步骤:
(1)式(VII)所示炔烯胺化合物与多聚甲醛发生加成反应,得到式(VI)所示炔丙醇化合物;
(2)式(VI)所示炔丙醇化合物发生氧化反应,得到式(V)所示炔醛化合物;
(3)式(V)所示炔醛化合物发生环丙烷化反应,得到式(IV)所示烯基环丙醛化合物;
(4)式(IV)所示烯基环丙醛化合物发生还原反应,得到式(III)所示环丙醛化合物;
(5)式(III)所示环丙醛化合物发生氧化反应,得到式(II)所示环丙羧酸化合物;
(6)式(II)所示的环丙羧酸化合物在溶剂中与铑金属催化剂发生配位反应,得到式(I)所示的手性双核铑金属催化剂;
优选地,步骤(1)中,反应可以如下进行:式(VII)所示炔烯胺化合物溶于四氢呋喃冷却至-78℃,滴入正丁基锂,搅拌1小时后加入多聚甲醛,持续搅拌升温至室温过夜,后分离得到式(VI)所示炔丙醇化合物;
优选地,步骤(2)中,反应可以如下进行:式(VI)所示炔丙醇化合物溶于二氯甲烷,加入戴斯马丁氧化剂进行氧化,后分离得到式(V)所示炔醛化合物;
优选地,步骤(3)中,反应可以如下进行:式(V)所示炔醛化合物溶于甲苯,加入铑催化剂进行环丙烷化反应,后分离得到式(IV)所示烯基环丙醛化合物;
优选地,步骤(4)中,反应可以如下进行:式(IV)所示烯基环丙醛化合物溶于二氯甲烷,加入三乙基硅烷和三氟乙酸,搅拌24小时后分离得到式(III)所示环丙醛化合物;如果有需要的话,可以用二氯甲烷和石油醚进行重结晶提高其ee值;
优选地,步骤(5)中,反应可以如下进行:式(III)所示环丙醛化合物溶于丙酮:叔丁醇:水=3:3:1的混合溶剂,加入2-甲基-2-丁烯、磷酸二氢钾和亚氯酸钠,搅拌2h,后分离得到式(II)所示环丙羧酸化合物;如果有需要的话,可以用二氯甲烷和石油醚进行进行重结晶提高其ee值;
优选地,步骤(6)中,反应可以如下进行:式(II)所示环丙羧酸化合物加入溶剂和对应的铑金属催化剂,加热反应后分离得到式(I)所示的手性双核铑金属催化剂。
优选地,所述铑金属催化剂选自醋酸铑或四(μ-碳酸化)二铑四钠。
优选地,所述溶剂选自苯、甲苯或水。
本发明所用式(VII)所示炔烯胺化合物可以直接购买或根据现有技术简单合成。
例如利用炔丙胺和烯丙基溴可制得N-烯丙基-4-甲基-N-(丙基-2-炔基-1-基)苯磺酰胺;
本发明手性双核铑金属催化剂在用于不对称反应中的用途也在本发明保护范围内。
本发明所述手性双核铑金属催化剂可以作为催化剂用于催化不对称反应,如烯烃的环丙烷化,碳氢、硅氢和硼氢插入等反应。
优选地,所述不对称反应为二炔化合物的不对称环异构化反应。
与现有技术相比,本发明具有如下有益效果:
本发明提供了一系列具有新型骨架的手性双核铑催化剂,扩大了催化剂库。该系列催化剂可以使不对称反应在温和的条件下进行,提高反应活性和对映选择性。
附图说明
图1为实施例1制备的催化剂I-1的结构图。
具体实施方式
以下结合说明书附图和具体实施例来进一步说明本发明,但实施例并不对本发明做任何形式的限定。除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1
催化剂I-1的制备
(1)-78℃氮气氛围下,将N-烯丙基-4-甲基-N-(丙基-2-炔基-1-基)苯磺酰胺(VII-1,40mmol)和超干四氢呋喃(150mL)加入至反应管,逐滴加入正丁基锂(60mmol)。反应1h后,加入多聚甲醛(200mmol),室温反应过夜,用饱和氯化铵淬灭,乙酸乙酯萃取三次,有机相再用饱和食盐水洗、无水硫酸钠干燥,旋蒸除去溶剂,得到的粗产品以石油醚和乙酸乙酯(PE/EA=2:1)作为流动相进行柱层析分离,得到式(VI-1)所示炔丙醇化合物(7.8g,70%)。
(2)室温空气氛围下,依次向烧瓶中加入式(VI-1)所示炔丙醇化合物(25mmol),二氯甲烷(250mL)和戴斯马丁氧化剂(30mmol),用薄层色谱监测原料全部转化后,用饱和的硫代硫酸钠和碳酸氢钠混合水溶液淬灭,待溶液澄清后,用二氯甲烷萃取三次,有机相再用饱和食盐水洗、无水硫酸钠干燥后,旋蒸除去溶剂,得到的粗产品以石油醚和乙酸乙酯(PE/EA=5:1)作为流动相进行柱层析分离,得到式(V-1)所示炔醛化合物(5.2g,75%)。
(3)室温氮气氛围下,将式(V-1)所示炔醛化合物(6.61mmol)和甲苯(25mL)加入至希莱克管中,然后将溶在2mL甲苯中的Rh2(S-BTPCP)4(0.1mol%)缓慢加入,用薄层色谱进行监测直到原料全部转化完,旋蒸除去溶剂,得到的粗产品以石油醚和乙酸乙酯(PE/EA=5:1)作为流动相进行柱层析分离,得到式(IV-1)所示烯基环丙醛化合物(1.65g,90%,91%ee)。
(4)室温空气条件下,将式(IV-1)所示烯基环丙醛化合物(5.9mmol)溶于60mL二氯甲烷中,依次加入三乙基硅烷(26mmol)和三氟乙酸(26mmol),24h后,用饱和碳酸氢钠水溶液淬灭,二氯甲烷萃取,得到的有机相用饱和食盐水洗涤、无水硫酸钠干燥,旋蒸除去溶剂,得到的粗产品以石油醚和乙酸乙酯(PE/EA=5:1)作为流动相进行柱层析分离,得到式(III-1)所示环丙醛化合物(1.22g,74%,91%ee)。用20mL二氯甲烷和20mL石油醚对其进行重结晶可得到对映体过量更高的环丙醛化合物(488mg,40%,98%ee)。
(5)室温空气氛围下,将式(III-1)所示环丙醛化合物(1.75mmol)溶于丙酮:叔丁醇:水=3:3:1组成的14mL混合溶剂中,再加入2-甲基-2-丁烯(8.75mmol),磷酸二氢钾(7mmol)和亚氯酸钠(5.25mmol)。2h后,用水和二氯甲烷萃取,有机相用饱和食盐水洗涤、无水硫酸钠干燥,旋蒸除去溶剂,得到的粗产品以二氯甲烷和甲醇(DCM/MeOH=40:1)作为流动相进行柱层析分离,得到式(II-1)所示环丙羧酸化合物(442mg,86%,98%ee))。1H NMR(500MHz,CDCl3)δ7.61(d,J=7.9Hz,2H),7.31(d,J=7.8Hz,2H),3.71(d,J=11.7Hz,1H),3.43–3.32(m,1H),2.87(dd,J=11.7,4.0Hz,1H),2.67(dt,J=14.5,4.2Hz,1H),2.42(s,3H),2.31(td,J=11.5,4.9Hz,1H),1.91–1.77(m,2H),1.52(dd,J=9.0,3.8Hz,1H),1.06–0.97(m,1H).13C NMR(125MHz,CDCl3)δ180.8,143.7,133.4,129.8,127.6,43.8,42.9,23.6,22.5,21.5,20.7,20.2.
(6)室温氮气氛围下,向希莱克管中加入四(μ-碳酸化)二铑四钠水合物(0.125mmol)、式(II-1)所示环丙羧酸化合物(295mg,1mmol)和8mL蒸馏水,110℃反应72h后,用二氯甲烷萃取,有机相用饱和食盐水洗涤、无水硫酸钠干燥,旋蒸除去溶剂,甲苯:乙腈=8:1作为流动相,柱层析分离得到催化剂I-1(140.5mg,80%,98%ee)。1H NMR(500MHz,CD3CN)δ7.58(d,J=8.3Hz,8H),7.39(d,J=8.1Hz,8H),3.34(d,J=11.8Hz,4H),3.07(dt,J=10.8,4.8Hz,4H),2.81(dd,J=11.8,4.8Hz,4H),2.43(s,16H),2.28(ddd,J=12.0,10.4,5.2Hz,4H),1.61(ddd,J=14.4,10.1,5.9Hz,4H),1.40–1.32(m,4H),0.93(dd,J=9.2,4.0Hz,4H),0.53(dd,J=6.4,4.2Hz,4H).13C NMR(100MHz,CD3CN)δ193.2,144.5,134.2,130.3,128.0,44.4,43.3,24.8,22.7,21.1,21.0,19.3.
实施例2
催化剂I-2的制备
以4-甲基-N-(2-甲基烯丙基)-N-(丙基-2-炔基-1-基)苯磺酰胺(VII-2)代替实施例1中的N-烯丙基-4-甲基-N-(丙基-2-炔基-1-基)苯磺酰胺,其余操作不变,得到催化剂I-2(152mg,83%,99%ee)。1H NMR(500MHz,CDCl3)δ7.58(d,J=8.0Hz,8H),7.31(d,J=7.9Hz,8H),3.53(d,J=11.8Hz,4H),3.37–3.28(m,4H),2.43(s,12H),2.29(d,J=11.8Hz,4H),2.25–2.17(m,8H),1.58(ddd,J=14.0,11.1,6.6Hz,4H),1.23(d,J=4.6Hz,4H),0.78(d,J=4.7Hz,4H),0.74(s,12H).13C NMR(125MHz,CDCl3)δ191.3,143.7,133.5,129.7,127.5,49.9,43.2,28.9,26.0,25.7,22.3,21.5,17.5.
实施例3
催化剂I-3的制备
以N-(3,3-二甲基-2-亚甲基丁基)-4-甲基-N-(丙基-2-炔-1-基)苯磺酰胺(VII-3)代替实施例1中的N-烯丙基-4-甲基-N-(丙基-2-炔基-1-基)苯磺酰胺,其余操作不变,得到催化剂I-3(132mg,65%,98%ee)。1H NMR(500MHz,CDCl3)δ7.52(d,J=7.8Hz,8H),7.23(d,J=7.7Hz,8H),3.15(d,J=12.4Hz,4H),3.01(d,J=12.3Hz,8H),2.75–2.62(m,4H),2.36(s,12H),2.07(dq,J=12.7,6.2Hz,4H),1.40(s,4H),1.28(dt,J=14.4,7.2Hz,4H),0.65(s,36H),0.51(s,4H).13C NMR(125MHz,CDCl3)δ193.5,143.4,134.2,129.7,127.2,46.4,42.3,39.2,33.5,30.1,28.6,28.5,21.5,18.2.
实施例4
催化剂I-4的制备
以N-(2(-(叔丁基二甲基硅基)氧基)甲基)烯丙基-4-甲基-N-(丙基-2-炔基-1-基)苯磺酰胺(VII-4)代替实施例1中的N-烯丙基-4-甲基-N-(丙基-2-炔基-1-基)苯磺酰胺,步骤1~5操作不变,得到环丙羧酸化合物(II-4,1.47g,96%,94%ee)。1H NMR(400MHz,CDCl3)δ7.71(d,J=8.1Hz,2H),7.39(d,J=8.0Hz,2H),3.85–3.69(m,3H),3.53(dt,J=10.3,4.5Hz,1H),2.96(d,J=11.7Hz,1H),2.75(dt,J=14.2,4.2Hz,1H),2.49(s,3H),2.38(td,J=11.3,4.8Hz,1H),1.90(ddd,J=14.3,11.1,6.0Hz,1H),1.61(d,J=4.7Hz,1H),1.16(d,J=4.8Hz,1H),0.84(s,9H),0.03(s,3H),-0.00(s,3H).13C NMR(100MHz,CDCl3)δ179.0,143.7,133.1,129.7,127.6,63.5,46.4,43.2,33.5,25.6,25.3,22.2,21.5,21.4,18.0,-5.69,-5.71.
室温氮气氛围下,向带有索氏提取器的反应瓶中加入醋酸铑(0.125mmol)、环丙羧酸化合物II-4(1mmol)和8mL甲苯,130℃反应72h后,旋蒸除去溶剂,甲苯:乙腈=8:1作为流动相,柱层析分离得到催化剂I-4(223mg,90%,94%ee)。1H NMR(400MHz,CDCl3)δ7.58(d,J=8.1Hz,8H),7.30(d,J=8.0Hz,8H),3.71(t,J=11.5Hz,4H),3.33–3.08(m,12H),2.58(dt,J=12.2,8.6Hz,4H),2.42(s,20H),1.61(dt,J=13.8,6.2Hz,4H),1.50–1.39(m,4H),1.32–1.24(m,4H),0.86(t,J=3.8Hz,36H),0.02–-0.07(m,24H).13C NMR(125MHz,CDCl3)δ191.0,143.6,133.6,129.7,127.5,64.3,47.0,42.7,31.8,27.9,25.84,25.75,21.6,21.5,18.1,-4.9,-5.1.
实施例5
催化剂I-5的制备
室温空气氛围下,将催化剂I-4(0.1mmol)和10mL四氢呋喃加入至反应瓶中,再加入四丁基氟化铵(0.8mmol),反应5分钟后,用水和二氯甲烷萃取三次,有机相用饱和食盐水洗涤、无水硫酸钠干燥,旋蒸除去溶剂,用二氯甲烷:甲醇=5:1作为流动相柱层析分离得到催化剂I-5(107mg,70%,94%ee)。1HNMR(500MHz,CD3CN)δ7.57(d,J=8.1Hz,8H),7.37(d,J=8.0Hz,8H),3.38(d,J=11.8Hz,4H),3.21(s,8H),3.16–3.09(m,4H),2.74(d,J=11.8Hz,4H),2.42(s,12H),2.37–2.31(m,8H),1.55(ddd,J=16.0,10.3,6.2Hz,4H),1.22(d,J=4.5Hz,4H),0.90–0.80(m,4H),0.68(d,J=4.6Hz,4H).13C NMR(125MHz,CD3CN)δ192.5,144.5,134.2,130.3,128.0,63.7,46.9,43.3,32.7,28.5,26.1,21.21,21.15.
实施例6
催化剂I-6的制备
以4-甲基-N-(2-苯基烯丙基)-N-(丙基-2-炔基-1-基)苯磺酰胺(VII-6)代替实施例1中的N-烯丙基-4-甲基-N-(丙基-2-炔基-1-基)苯磺酰胺,其余操作不变,得到催化剂I-6(160mg,75%,98%ee)。1H NMR(500MHz,CDCl3)δ7.54(d,J=8.1Hz,8H),7.27(d,J=8.1Hz,8H),7.14(q,J=7.7,6.4Hz,12H),6.86(d,J=7.4Hz,8H),3.61(d,J=11.9Hz,4H),3.45(ddd,J=11.3,6.9,3.3Hz,4H),2.63(d,J=11.9Hz,4H),2.52(ddd,J=14.1,5.6,3.4Hz,4H),2.40(d,J=7.5Hz,16H),1.77–1.71(m,4H),1.45(d,J=4.0Hz,4H),1.14(d,J=3.9Hz,4H).13C NMR(125MHz,CDCl3)δ189.3,143.7,140.1,133.7,129.8,129.3,128.0,127.4,126.7,51.7,43.4,36.5,29.5,25.0,23.2,21.6.
实施例7
催化剂I-7的制备
以N-(2-(4-氟苯基)烯丙基)-4-甲基-N-(丙基-2-炔-1-基)苯磺酰胺(VII-7)代替实施例1中的N-烯丙基-4-甲基-N-(丙基-2-炔基-1-基)苯磺酰胺,其余操作不变,得到催化剂I-7(144mg,59%,99%ee)。1H NMR(500MHz,CDCl3)δ7.55(d,J=8.2Hz,8H),7.28(d,J=8.3Hz,8H),6.86–6.78(m,16H),4.15(q,J=7.1Hz,4H),3.53(d,J=12.0Hz,4H),3.47–3.36(m,4H),2.66(d,J=12.0Hz,4H),2.47(td,J=12.3,10.5,4.9Hz,8H),2.40(s,12H),2.01(s,6H),1.74–1.63(m,4H),1.42(d,J=4.1Hz,4H),1.28(t,J=7.1Hz,6H),1.15(d,J=4.3Hz,4H).13C NMR(125MHz,CDCl3)δ189.3,172.3,161.4(d,J=245.6Hz),143.8,135.6(d,J=2.9Hz),133.6,130.6(d,J=7.9Hz),129.83,129.77,127.4,114.9(d,J=21.2Hz),60.8,51.8,43.2,35.5,29.7,25.1,23.1,21.5,21.0,14.2.19F NMR(471MHz,CDCl3)δ-114.89.
实施例8
催化剂I-8的制备
以N-(2-(4-溴苯基)烯丙基)-4-甲基-N-(丙基-2-炔-1-基)苯磺酰胺(VII-8)代替实施例1中的N-烯丙基-4-甲基-N-(丙基-2-炔基-1-基)苯磺酰胺,其余操作不变,得到催化剂I-8(197mg,78%,99%ee)。1H NMR(500MHz,CDCl3)δ7.55(d,J=8.1Hz,8H),7.29(d,J=8.0Hz,16H),6.78(d,J=8.2Hz,8H),3.57(d,J=12.0Hz,4H),3.49–3.42(m,4H),2.62(d,J=11.9Hz,4H),2.57–2.50(m,4H),2.48–2.43(m,4H),2.41(s,12H),1.72(ddd,J=14.3,10.3,7.1Hz,4H),1.48(d,J=4.0Hz,4H),1.24(d,J=4.2Hz,4H).13C NMR(125MHz,CDCl3)δ189.3,143.9,139.0,133.4,131.2,130.9,129.9,127.5,120.7,51.7,43.4,36.1,29.7,24.6,23.3,21.6.
实施例9
催化剂I-9的制备
室温氮气氛围下,将取催化剂I-8(0.02mmol),3,5-二甲基苯硼酸(0.16mmol),磷酸钾(0.24mmol)和四氢呋喃:水=4:1组成的混合溶剂3.75mL加入至希莱克管中,加热回流10分钟除气,随后加入钯催化剂Pd(dppf)Cl2(0.008mmol),回流状态下反应24h,用二氯甲烷萃取,有机相用饱和食盐水洗涤、无水硫酸钠干燥,旋蒸除去溶剂,甲苯:乙腈=8:1作为流动相,柱层析分离得到催化剂9(21.3mg,50%,99%ee)。1H NMR(400MHz,CDCl3)δ7.53(d,J=8.1Hz,4H),7.31–7.21(m,24H),7.08(s,4H),6.84(d,J=7.9Hz,8H),3.66(d,J=11.9Hz,4H),3.46–3.35(m,4H),2.61(d,J=11.9Hz,8H),2.46(s,24H),2.41(s,12H),2.33(dt,J=11.7,6.1Hz,4H),1.85–1.71(m,4H),1.59(d,J=3.3Hz,4H),1.25(d,J=3.8Hz,4H).13C NMR(125MHz,CDCl3)δ189.3,143.7,140.5,139.6,139.0,138.3,133.6,129.8,129.5,129.1,127.4,126.6,124.9,51.8,43.5,36.8,29.3,24.6,23.8,21.6.
实施例10
催化剂I-10的制备
以3,5-二叔丁基苯硼酸代替实施例9的3,5-二甲基苯硼酸,其余操作不变,得到催化剂I-10(23.1mg,47%,99%ee)。1HNMR(500MHz,CDCl3)δ7.50(d,J=7.9Hz,8H),7.44(s,4H),7.38(d,J=2.0Hz,8H),7.29(d,J=7.8Hz,8H),7.23(d,J=7.9Hz,8H),6.85(d,J=7.8Hz,8H),3.60(d,J=11.9Hz,4H),3.36–3.30(m,4H),2.61(t,J=12.9Hz,8H),2.38(s,12H),2.31(td,J=11.6,5.6Hz,4H),1.73–1.69(m,4H),1.52(d,J=3.8Hz,4H),1.16(d,J=4.2Hz,4H).13CNMR(125MHz,CDCl3)δ189.5,151.2,143.6,140.7,139.9,138.8,134.0,129.8,129.4,127.4,126.9,121.5,121.4,51.7,43.3,36.7,35.0,31.6,31.5,29.4,24.9,23.8,21.5.
实施例11
催化剂I-11的制备
以3,5-苯基苯硼酸代替实施例9的3,5-二甲基苯硼酸,其余操作不变,得到催化剂I-11(35.6mg,68%,99%ee)。1HNMR(500MHz,CDCl3)δ7.72(s,4H),7.68(s,8H),7.64(d,J=7.5Hz,16H),7.46(t,J=7.6Hz,16H),7.38(t,J=7.4Hz,8H),7.35(d,J=8.0Hz,8H),7.30(d,J=7.8Hz,8H),7.07(d,J=8.0Hz,8H),6.89(d,J=7.8Hz,8H),3.56(d,J=11.9Hz,4H),3.25(t,J=9.7Hz,4H),2.60(dd,J=17.9,12.5Hz,8H),2.31(s,16H),1.73–1.68(m,4H),1.58(d,J=4.0Hz,4H),1.22(d,J=4.2Hz,4H).13CNMR(125MHz,CDCl3)δ189.4,143.5,142.5,141.6,141.0,139.5,139.4,133.5,129.7,129.6,128.9,127.7,127.4,127.3,126.8,125.3,124.9,51.9,43.4,36.7,29.7,29.5,24.7,24.0,21.5.
实施例12
采用下述反应检测本发明制备的催化剂与市售铑的手性催化剂效果
具体操作:氮气保护氛围下,取S1所示三炔化合物(0.2mmol),加入1.9ml甲苯,加入1%的催化剂(溶于0.1ml甲苯中),25℃搅拌48小时。反应结束后旋干溶剂,用石油醚和乙酸乙酯(PE/EA=5:1)作为流动相进行柱层析分离,得到P1所示化合物。1H NMR(500MHz,CDCl3)δ7.03(s,1H),6.35(d,J=5.8Hz,1H),5.67(d,J=5.9Hz,1H),1.76(s,3H),1.45(s,9H),1.27(s,9H).13C NMR(125MHz,CDCl3)δ155.7,140.6,130.8,116.8,114.6,96.1,94.3,81.3,72.9,34.0,30.6,30.3,29.9,27.5.
本发明制备的催化剂与市售铑催化剂的对比结果见表1。
表1
序号 | 催化剂 | 收率 | ee值 |
1 | Rh<sub>2</sub>(R-PTAD)<sub>4</sub> | 3% | 17% |
2 | Rh<sub>2</sub>(S-PTPA)<sub>4</sub> | 21% | 0 |
3 | Rh<sub>2</sub>(S-DOSP)<sub>4</sub> | 29% | 23% |
4 | Rh<sub>2</sub>(S-BTPCP)<sub>4</sub> | 3% | 19% |
5 | Rh<sub>2</sub>(S-TCPTTL)<sub>4</sub> | 0% | - |
6 | Rh<sub>2</sub>(S-TFFPTTL)<sub>4</sub> | 2% | 26% |
7 | Rh<sub>2</sub>(S-PTTL)<sub>4</sub> | 4% | 26% |
8 | Rh<sub>2</sub>(S-NTTL)<sub>4</sub> | 49% | 44% |
9 | Rh<sub>2</sub>(R-p-PhTPCP)<sub>4</sub> | 67% | 27% |
10 | 催化剂I-8 | 5% | 12% |
11 | 催化剂I-9 | 78% | 66% |
12 | 催化剂I-10 | 54% | 48% |
13 | 催化剂I-11 | 18% | 53% |
结果表明,本发明的系列催化剂具有一定的催化不对称反应的效果。部分催化效果与市售催化剂相近,个别催化剂效果要更优。
实施例13
采用下述反应检测本发明制备的催化剂的手性催化剂效果
具体操作:氮气保护氛围下,取S2所示三炔化合物(0.2mmol),加入1.9ml甲苯,加入1%的催化剂(溶于0.1ml甲苯中),25℃搅拌48小时。反应结束后旋干溶剂,用石油醚和乙酸乙酯(PE/EA=5:1)作为流动相进行柱层析分离,得到P2所示化合物。1H NMR(400MHz,CDCl3)δ7.65–7.55(m,2H),7.39–7.31(m,3H),7.22(s,1H),6.30(d,J=5.9Hz,1H),5.73(d,J=5.8Hz,1H),1.35(s,9H),1.18(s,9H).13C NMR(100MHz,CDCl3)δ157.1,143.4,140.7,131.3,128.4,128.0,127.3,117.3,113.1,97.3,95.3,80.0,76.5,34.0,30.6,29.4,27.8.
本发明制备的催化剂与市售铑催化剂的对比结果见表2。
表2
序号 | 催化剂 | 收率 | ee值 |
1 | Rh<sub>2</sub>(S-PTTL)<sub>4</sub> | 42% | 17% |
2 | Rh<sub>2</sub>(S-TCPTTL)<sub>4</sub> | 14% | 25% |
3 | Rh<sub>2</sub>(S-TFFPTTL)<sub>4</sub> | 14% | 24% |
4 | Rh<sub>2</sub>(S-NTTL)<sub>4</sub> | 66% | 33% |
5 | Rh<sub>2</sub>(S-BTPCP)<sub>4</sub> | 42% | 12% |
6 | 催化剂I-1 | 74% | 2% |
7 | 催化剂I-2 | 50% | 5% |
8 | 催化剂I-3 | 38% | 21% |
9 | 催化剂I-4 | 25% | 9% |
10 | 催化剂I-6 | 15% | 5% |
11 | 催化剂I-7 | 22% | 8% |
12 | 催化剂I-9 | 62% | 57% |
结果表明,本发明的系列催化剂具有一定的催化不对称反应的效果。部分催化效果与市售催化剂相近,个别催化剂效果要更优。
实施例14
催化剂I-1的结构图如图1;
催化剂I-1的单晶数据如下:
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (10)
2.根据权利要求1所述的手性双核铑金属催化剂,其特征在于,
所述取代的C1~C6直链或支链烷基任意一个或多个氢原子被羟基或被保护基保护的羟基取代;
所述取代的C6~14芳基上任意一个或多个氢原子被取代基取代,所述取代基选自卤素、C1~6直链或支链烷基或取代或未取代的苯基;所述取代的苯基上任意一个或多个氢原子被C1~C6直链或支链烷基、卤素或苯基取代。
3.根据权利要求1所述的手性双核铑金属催化剂,其特征在于,R1选自氢、C1~C6直链或支链烷基或苯基。
4.根据权利要求2所述的手性双核铑金属催化剂,其特征在于,所述保护基为叔丁基二甲基硅基。
8.根据权利要求6所述制备方法,其特征在于,所述铑金属催化剂选自醋酸铑或四(μ-碳酸化)二铑四钠。
9.根据权利要求6所述制备方法,其特征在于,所述溶剂选自苯、甲苯或水。
10.权利要求1-5任一所述手性双核铑金属催化剂的应用,其特征在于,将手性双核铑金属催化剂用于不对称反应。
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