CN113150025B - 一种硅中心手性硅氧化合物及其制备方法 - Google Patents
一种硅中心手性硅氧化合物及其制备方法 Download PDFInfo
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- CN113150025B CN113150025B CN202110258147.0A CN202110258147A CN113150025B CN 113150025 B CN113150025 B CN 113150025B CN 202110258147 A CN202110258147 A CN 202110258147A CN 113150025 B CN113150025 B CN 113150025B
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- 230000005540 biological transmission Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
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- 229910052794 bromium Inorganic materials 0.000 description 1
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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Abstract
本发明属于手性硅合成领域,公开了一种硅中心手性硅氧化合物,其具有通式Ⅰ的结构:X为Si(R3)n或其中,R1选自烷基、环烷基、芳基,R2选自烷基、取代苯基、芳基,R3选自烷基、苯基、取代苯基、n为3,所存在的3个R3相同或不同,R4选自氢、(C1‑C4)烷基,m选自0、1、2、3,Y选自取代苯基、取代芘基、芳基、杂芳基、环烷基、 本发明还公开了该类化合物的制备方法。本发明以良好的化学、区域和立体控制,高收率获得各种高度官能化的手性硅氧烷和硅醚,扩展了硅中心手性化合物的种类,具有对应选择性高、底物适用范围广、反应条件温和、原子经济等优点。此外,本发明的化合物在手性有机光电材料中具有巨大的应用前景。
Description
技术领域
本发明属于手性硅合成领域,具体是一种硅中心手性硅氧化合物及其制备方法。
背景技术
含硅分子广泛应用于许多领域,在学术和工业上具有重要的意义。在过去几十年里,合成新型有机硅化合物的方法得到了发展,使含硅分子在有机化学、有机金属化学和高分子化学中得到了广泛应用。其中,硅氧烷和硅醚是硅基材料的重要结构,可作为有机合成的保护基、试剂和中间体。尽管已有很多合成硅氧烷和硅醚的方法,但获得硅手性中心化合物的方法还很鲜有报道,这限制了手性硅化合物的设计和应用。
目前,可以通过手性醇助剂的光学拆分和动力学拆分得到硅手性硅醚,但是底物范围有限,效率低且原子经济性差,其他的一些方法则无法获得满意的ee值。考虑到硅手性化合物的应用前景,需要探索新的合成方法,以便高效、对映选择性地获得此类化合物。
发明内容
本发明的目的是提供一类结构新颖的硅中心手性硅氧烷和硅醚化合物。
本发明的另一目的是提供该类化合物的制备方法。
为达到上述目的之一,本发明采用以下技术方案:
一种硅中心手性硅氧化合物,其具有通式I的结构:
其中,R1选自烷基、环烷基、芳基,
R2选自烷基、取代苯基、芳基,
n为3,所存在的3个R3相同或不同,比如R3均为甲基或苯基,则X为SiMe3、SiPh3;比如R3分部为一个甲基、两个苯基,则X为SiMePh2;比如R3分部为两个甲基、一个苯基,则X为SiMe2Ph。
R4选自氢、(C1-C4)烷基,
m选自0、1、2、3,
进一步地,所述R1选自烷基、环烷基、苯基、萘基、蒽基、菲基。
进一步地,所述R2选自苯基、烷基苯基、吗啉基苯基、卤代苯基、烷氧基苯基、三氟甲基苯基、萘基、蒽基、菲基、芘基。
进一步地,所述R1选自(C1-C4)烷基、环丙基、环丁基、环戊基、环己基、苯基、萘基、蒽基、菲基。
进一步地,所述R2选自苯基、吗啉基苯基、卤代苯基、烷氧基苯基、萘基、蒽基、菲基、芘基。
进一步地,所述R1选自甲基、乙基、丙基、丁基、环丙基、环丁基、环戊基、环己基、萘基。
进一步地,所述R2选自苯基、吗啉基苯基、氟代苯基、氯代苯基、溴代苯基、碘代苯基、甲氧基苯基、萘基、芘基。
进一步地,所述R1选自甲基、丙基、丁基、环己基、萘基。
进一步地,所述R2选自苯基、吗啉基苯基、氟代苯基、甲氧基苯基、萘基、芘基。
进一步地,所述R1选自甲基、异丙基、叔丁基、环己基、1-萘基。
进一步地,所述R2选自苯基、4-吗啉基苯基、4-氟代苯基、4-甲氧基苯基、1-萘基、1-芘基。
进一步地,Si(R3)n选自-SiMe2Ph、-SiMe2(4-OMe-C6H4)、-SiMe2(4-Cl-C6H4)、-SiMe2(2-F-C6H4)、-SiMePh2、-SitBuPh2、-SiMe3、
进一步地,所述R4选自氢、甲基。
进一步地,所述Y选自苯基、烷基苯基、卤代苯基、三氟甲基苯基、烷氧基苯基、萘基、蒽基、菲基、芴基、芘基、呋喃基、噻吩基、吡咯基、苯并呋喃基、吲哚基、咪唑基、吡唑基、唑基、噻唑基、吡啶基、喹啉基、环丙基、环丁基、环戊基、环己基、1,3-苯并二恶唑基、吩噻嗪基、
进一步地,所述Y选自苯基、甲基苯基、氟代苯基、溴代苯基、三氟甲基苯基、甲氧基苯基、萘基、芴基、芘基、呋喃基、噻吩基、环己基、1,3-苯并二恶唑基、吩噻嗪基、
当R4选自甲基,m为1时,Y选自苯基;
当R4选自氢,m为2时,Y选自甲氧基苯基、甲基苯基、氟代苯基、噻吩基;
当R4选自氢,m为3时,Y选自环己基。
进一步地,通式I化合物为以下化合物中的一种:
通式I化合物的制备方法,包括以下步骤:在配体和铑催化剂存在下,式II化合物和(R3)3SiOH或R4OH反应如下:
所述铑催化剂选自[Rh(cod)Cl]2、[Rh(cod)OH]2、[Rh(nbd)Cl]2或[Rh(CO)2Cl]2;
所述配体选自以下化合物:
R、R’各自独立地选自叔丁基、环己基、苯基、3,5-二甲基-4-甲氧基苯基、3,5-二三氟甲基苯基;
R1、R2、R3、R4如前文所定义。
进一步地,所述铑催化剂为[Rh(cod)Cl]2。
进一步地,所述配体选自以下化合物:
进一步地,所述配体的用量至少是2mol%,所述铑催化剂的用量至少是1mol%;配体、铑催化剂的用量的基准是相对于原料(R3)3SiOH或R4OH化合物的用量,比如,配体的用量写成2mol%的形式,指每1mol(R3)3SiOH或R4OH使用0.02mol配体;铑催化剂的用量写成1mol%的形式,指每1mol(R3)3SiOH或R4OH使用0.01mol铑催化剂。
进一步地,所述式II化合物和(R3)3SiOH或R4OH的摩尔比为(1~3)∶1。
进一步地,所述反应以甲苯、乙腈、二氯乙烷或1,4-二氧六环为溶剂。
进一步地,所述反应的温度为0℃以上。
进一步地,所述反应的时间至少为12h。
本文所用的“烷基”指饱和脂肪族烃基团,其为包含1至20个碳原子的直链或支链基团,优选含有1至12个碳原子的烷基,更优选含有1至6个碳原子的烷基。烷基基团的实例包括甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、戊基、2-戊基、异戊基、新戊基、己基、2-己基、3-己基、3-甲基戊基。
本文所用的“环烷基”指非芳族碳环,其通常具有3至8个环碳原子。所述环可以是饱和的或具有一个或更多个碳-碳双键。环烷基基团的实例包括环丙基、环丁基、环戊基、环戊烯基、环己基和环己烯基。
本文所用的“烷氧基”指-O-(烷基)和-O-(环烷基),其中烷基、环烷基的定义如本文所述,烷氧基的非限制性实例包括:甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、仲丁氧基、叔丁氧基、戊氧基、2-戊氧基、异戊氧基、新戊氧基、己氧基、2-己氧基、3-己氧基、3-甲基戊氧基、环丙氧基、环丁氧基、环戊氧基、环己氧基。烷氧基基团通常具有通过氧桥连接的1至7个碳原子。
本文所用的“卤素”指氟、氯、溴和碘。
本文所用的“三氟甲基”指-CF3。
本文所用的“取代苯基”指被其他官能团(例如卤素、三氟甲基、烷氧基、烷基、吗啉基、)所取代的苯基,可以是单取代,也可以是多取代,当存在2个以上取代基时,取代基的种类可以相同或不同。
本文所用的“芳基”指6元碳环芳族环,包括单环体系,如苯基;双环体系,其中至少一个环是碳环的和芳族的,如萘、茚满和1,2,3,4-四氢化萘;和三环体系,其中至少一个环是碳环的和芳族的,如芴。
例如,芳基包括与5元至7元杂环烷基环稠合的6元碳环芳族环,所述杂环烷基环含有选自N、O和S的一个或更多个杂原子。对于其中只有一个环是碳环芳族环的此类稠合双环体系,连接点可以在碳环芳族环或杂环烷基环上。将形成自取代的苯衍生物且在环原子上具有自由价的二价基团称为取代的亚苯基基团。从其名称以“基”结尾的一价多环烃基团中通过从具有自由价的碳原子上去除一个氢原子而衍生的二价基团通过在相应的一价基团的名称上加上“亚”来命名,如具有两个连接点的萘基基团称为亚萘基。然而,芳基不以任何方式包括杂芳基或与杂芳基重叠,杂芳基单独定义如下。因此,如果一个或更多个碳环芳族环与杂环烷基芳族环稠合,则所得环体系是杂芳基而不是芳基,如本文所定义。
典型的芳基为苯基、萘基、蒽基、菲基、芴基,芳基可以在任意的位置与骨架结构相连。
本文所用的“杂芳基”指:
5元至7元芳族单环,其含有一个或更多个(如1至4个,或在某些实施方案中是1至3个)选自N、O和S的杂原子且其余环原子是碳;
双环杂环烷基环,其含有一个或更多个(如1至4个,或在某些实施方案中是1至3个)选自N、O和S的杂原子且其余环原子是碳,且其中至少一个杂原子存在于芳族环中;
和三环杂环烷基环,其含有一个或更多个(如1至5个,或在某些实施方案中是1至4个)选自N、O和S的杂原子且其余环原子是碳,且其中至少一个杂原子存在于芳族环中;
例如,杂芳基包括与5元至7元环烷基或杂环烷基环稠合的5元至7元杂环烷基芳族环。对于其中只有一个环含有一个或更多个杂原子的此类稠合双环杂芳基环体系,连接点可以在任一环上。当杂芳基基团中S和O原子的总数超过1时,这些杂原子彼此不相邻。在某些实施方案中,杂芳基基团中S和O原子的总数不超过2。在某些实施方案中,芳族杂环中S和O原子的总数不超过1。
杂芳基基团的实例包括但不限于(从指定为1位的连接位置编号)2-吡啶基、3-吡啶基、4-吡啶基、2,3-吡嗪基、3,4-吡嗪基、2,4-嘧啶基、3,5-嘧啶基、2,3-吡唑啉基、2,4-咪唑啉基、异噁唑啉基、噁唑啉基、噻唑啉基、噻二唑啉基、四唑基、噻吩基、苯并噻吩基、呋喃基、苯并呋喃基、苯并咪唑啉基、二氢吲哚基、哒嗪基、三唑基、喹啉基、吡唑基、咪唑基、噻唑基、噁唑基、吡咯基、吩噻嗪基、1,3-苯并二恶唑基和5,6,7,8-四氢异喹啉基。从其名称以“基”结尾的一价杂芳基基团中通过从具有自由价的原子上去除一个氢原子而得到的二价基团通过在相应的一价基团的名称上加上“亚”来命名,如具有两个连接点的吡啶基基团是亚吡啶基。杂芳基不包括芳基、环烷基或杂环烷基或不与芳基、环烷基或杂环烷基重叠,如本文所定义。
本发明具有以下有益效果:
本发明提供了铑催化对映选择性构建三取代硅手性中心的硅氧烷和硅醚的方法,通过二氢硅烷与硅烷醇或烷醇直接的分子间脱氢Si-O偶联,以良好的化学、区域和立体控制,高收率获得各种高度官能化的手性硅氧烷和硅醚,大大扩展了硅中心手性化合物的种类;具有对应选择性高、底物适用范围广、反应条件温和、原子经济等优点。
通过该方法可以构建CPL(圆偏振发光)活性的硅手性的硅醚有机小分子,其中,含有两个硅立体异构中心和三个芘基的光学纯的双烷氧基硅烷具有优异的g1um值和很高的荧光量子效率(glum:0.011,ΦF:0.55),本发明的化合物在手性有机光电材料中具有巨大的应用前景。
附图说明
图1是实施例33化合物5o的晶体结构;
图2是实施例41化合物6a~6c的光物理性质图谱;其中,(a)为化合物6a-6c的荧光图像;(b)为化合物6a-6c在CH2Cl2(10-5M)中的吸收光谱;(c)为化合物6a-6c在CH2Cl2(10-3M)中的发射光谱;(d)为化合物6a-6c及其对映异构体在室温、CH2Cl2(10-5M)中CD光谱;(e)为化合物6a-6c及其对映异构体在室温下、CH2Cl2(10-3M)中、349nm激发的CPL光谱;(f)为6a-6c及其对映异构体的glum值波长曲线。
具体实施方式
除非另有说明,所有反应均在惰性氩气保护下进行。通过在预涂覆的60F254硅胶板上进行薄层色谱法(TLC)监控反应,并使用紫外光(254nm)对色谱显色。使用GENERAR-REAGENT硅胶(200~300目)进行硅胶柱色谱。无水溶剂从Inert Pure Solv溶剂纯化系统获得,或者从Energy Chemical购买,所有试剂均购自商业供应商(Bide Pharmatech,Aladdin,Energy Chemical,Adamas和TCI),无需进一步纯化即可使用。核磁共振(NMR)光谱是在环境温度下使用Bruker DPX 400(400MHz)或Bruker DPX 600(600MHz)仪器记录。1HNMR(400或600MHz)化学位移参考四甲基硅烷信号(TMS:δ0ppm),13C NMR(101或151MHz)化学位移(CDCl3:δ77.16ppm,DMSO-d6:39.52ppm)使用CDCl3或DMSO-d6作为内标。以下缩写的含义为:s表示单峰,d表示双峰,t表示三重峰,q表示四重峰,m表示多重峰。在电喷雾电离(ESI)或大气压化学电离(APCI)条件下,在Agilent Technologies 6230TOF LC/MS或Thermo Scientific Q Exactive上记录高分辨率质谱(HRMS)。使用Bruker D8 VENTURE记录X射线晶体学数据。在Agilent 1260Infinity II上进行HPLC分析,手性柱OJ-3,AD-3,AD-H,IB,OD-3从Daicel购买。其中一些产物是将硅烷氧化为硅烷醇,以确保分离对映体、进行HPLC分析。用UV-Vis分光光度计(Shimadzu,UV3600)测量吸收光谱,用Shimadzu RF-6000光谱仪测量发射光谱,用JASCO CPL-300光谱仪测量圆偏振发光(CPL)光谱,用APPLIEDPHOTOPHYSICS Chirascan CD光谱仪上测量圆二色性(CD)光谱,用爱丁堡FLS 1000测量绝对荧光量子产率。
实施例1
二氢硅烷底物的合成
方法A:在-78℃、氩气保护下,向芳基溴(1.0当量)的THF(0.5M)溶液中滴加tBuLi(1.3M戊烷的溶液,1.1当量),在-78℃下搅拌1h,然后加入在10mL THF中的tBuSiCl3(1.2当量)。混合物在-78℃下再搅拌1h,然后温热至室温并搅拌过夜。将反应再次冷却至-78℃,并滴加LiAlH4(2.5M的THF溶液,2.0当量),并在-78℃下再搅拌30min,然后将混合物温热至室温并搅拌8h。最后将反应混合物在-78℃下用饱和NH4Cl淬灭,升至室温后,将混合物过滤,用Et2O洗涤,将有机层合并并用MgSO4干燥、过滤、减压蒸发。粗混合物通过硅胶柱色谱法纯化(100%石油醚),得到二氢硅烷。
方法B:在0℃、氩气保护下,向苯三氯硅烷(20mmol)的THF(40mL)溶液中滴加tBuLi(1.3M的戊烷溶液,1.1当量),混合物在0℃搅拌1h,然后温热至室温并搅拌8h,将反应冷却至0℃,并滴加LiAlH4(2.5M的THF溶液,2.0当量),并在0℃下搅拌30min。然后将混合物温热至室温并再搅拌8h,最后,将反应混合物在0℃下用饱和NH4Cl淬灭,升至室温后,将混合物过滤,用Et2O洗涤,将有机层合并并用MgSO4干燥、过滤、减压蒸发。
粗混合物通过硅胶柱色谱法纯化(100%石油醚),得到二氢硅烷。
按照方法A制备,产物1a为无色液体(Rf=0.7,石油醚),产率为74%(720mg)。表征数据:1H NMR(400MHz,CDCl3)δ7.49(d,J=8.4Hz,2H),6.91(d,J=4.8Hz,2H),4.12(s,2H),3.82(s,3H),1.00(s,9H)。13C NMR(151MHz,CDCl3)δ161.02,137.51,123.10,113.80,55.16,27.52,16.60。HRMS(ESI,m/z)精确质量计算C11H19OSi[M+H+]:195.1200,实测值:195.1224。
按照方法A制备,产物lb为白色固体(Rf=0.3,石油醚/乙酸乙酯=20∶1),产率为40%(300mg)。表征数据:1H NMR(400MHz,CDCl3)δ7.47(d,J=8.4Hz,2H),6.90(d,J=8.8Hz,2H),4.11(s,2H),3.86(t,J=4.8Hz,4H),3.20(t,J=4.8Hz,4H),1.00(s,9H)。13C NMR(101MHz,CDCl3)δ152.18,137.22,121.57,114.75,67.00,48.64,27.54,16.66。HRMS(ESI,m/z)精确质量计算C14H24NOSi[M+H+]:250.1622,实测值:250.1617。
按照方法A制备,产物1c为无色油状物(Rf=0.8,石油醚),收率为55%(300mg)。表征数据:1H NMR(400MHz,CDCl3)δ7.56-7.52(m,2H),7.08-7.04(m,2H),4.14(s,2H),1.00(s,9H)。13C NMR(101MHz,CDCl3)δ164.28(d,JCF=248.8Hz),137.97(d,JCF=7.7Hz),127.80(d,JCF=4.0Hz),115.27(d,JCF=19.7Hz),27.46,16.51。19F NMR(376MHz,CDCl3)δ-111.00。HRMS(ESI,m/z)精确质量计算C10H16FSi[M+H+]:183.1000,实测值:183.1020。
按照方法B制备,产物1d为无色液体(Rf=0.8,石油醚),收率为53%(1.74g)。表征数据:1H NMR(600MHz,CDCl3)δ7.57(d,J=7.2Hz,2H),7.41-7.25(m,3H),4.15(s,2H),1.02(s,9H)。13C NMR(151MHz,CDCl3)δ136.04,132.38,129.68,127.96,27.58,16.56。HRMS(ESI,m/z)精确质量计算C10H17Si[M+H+]:165.1094,实测值:165.1069。
按照方法A制备,产物1e为无色油状物,与萘(n/n=2∶1)混合不能分离(Rf=0.7,石油醚),收率为60%(423mg)。表征数据:1H NMR(400MHz,CDCl3)δ8.14(d,J=7.7Hz,1H),7.89(d,J=8.4Hz,1H),7.84(d,J=1.5Hz,1H),7.78(d,J=6.8Hz,1H),7.49-7.46(m,3H),4.52(s,2H),1.05(s,9H)。13C NMR(101MHz,CDCl3)δ137.63,137.17,133.60,131.30,130.62,128.90,128.87,126.13,125.80,125.16,28.27,17.49。HRMS(ESI,m/z)精确质量计算C14H19Si[M+H+]:215.1250,实测值:215.1289。
按照方法A制备,产物1f为浅黄色固体(Rf=0.7,石油醚),收率为47%(690mg)。表征数据:1H NMR(600MHz,CDCl3)δ8.40(d,J=9.0Hz,1H),8.23(d,J=7.2Hz,1H),8.17(t,J=7.8Hz,2H),8.13-8.07(m,3H),8.04-7.98(m,2H),4.72(s,2H),1.08(s,9H)。13C NMR(151MHz,CDCl3)δ136.60,135.47,132.80,131.38,130.90,128.49,128.38,128.29,127.62,127.61,126.05,125.44,125.41,124.78,124.63,124.12,28.22,17.85。HRMS(APCI,m/z)精确质量计算C20H21Si[M+H+]:289.1407,实测值:289.1418。
方法C:在0℃下,向搅拌的氯苯基硅烷(7.5mmol,1.5当量)的THF(15mL)溶液中加入R-MgBr(5.0mmol,1.0M在THF中的溶液,1.0当量),然后反应混合物温热至室温并搅拌2h,溶液冷却至0℃后,加入饱和NH4Cl溶液,混合物用Et2O萃取3次,合并的有机层经MgSO4干燥、减压蒸发。粗混合物通过硅胶柱色谱法纯化(100%石油醚),得到二氢硅烷。
按照方法C制备,产物1g为无色油状物(Rf=0.8,石油醚),收率为88%(660mg)。表征数据:1H NMR(400MHz,CDCl3)δ7.57(dd,J=7.6,1.5Hz,2H),7.41-7.33(m,3H),4.18(d,J=2.9Hz,2H),1.26-1.16(m,1H),1.08(d,J=7.2Hz,6H)。13C NMR(151MHz,CDCl3)δ135.71,132.35,129.65,128.05,18.98,10.84。
按照方法C制备,产物1h为无色油状物(Rf=0.8,石油醚),收率为78%(741mg)。表征数据:1H NMR(400MHz,CDCl3)δ7.55(dd,J=7.0,1.9Hz,2H),7.39-7.34(m,3H),4.16(d,J=2.9Hz,2H),1.78-1.68(m,6H),1.25-1.21(m,4H),1.11-1.09(m,1H)。13C NMR(151MHz,CDCl3)δ135.76,132.27,129.59,128.03,28.99,27.79,26.75,22.28。
按照方法C制备,产物1i为无色油状物(Rf=0.7,石油醚),收率为66%(765mg)。表征数据:1H NMR(400MHz,CDCl3)δ8.03-8.02(m,1H),7.93(d,J=8.4Hz,1H),7.87-7.86(m,1H),7.82-7.80(m,1H),7.61-7.60(m,2H),7.49-7.33(m,6H),5.24(s,2H)。13C NMR(151MHz,CDCl3)δ137.37,136.95,135.81,133.29,131.57,131.08,130.14,130.00,128.98,128.30,128.09,126.50,126.00,125.45。
实施例2
硅烷醇和醇底物的合成
方法D:在-78℃、氩气保护下,向芳基溴(1.0当量)的THF(0.5M)溶液中滴加nBuLi(2.5M的己烷溶液,1.1当量),混合物在-78℃下搅拌1h,加入氯二甲基硅烷(1.2当量),混合物在-78℃下搅拌1h,然后温热至室温并搅拌过夜。最后,将反应混合物在-78℃下用饱和NH4Cl淬灭,升至室温后,将混合物过滤,用Et2O洗涤,将有机层合并、用MgSO4干燥、过滤、减压蒸发,得到相应的产物,不经进一步纯化直接用于下一步。
方法E:在空气气氛下,向硅烷在THF(0.5M)的溶液中添加KMnO4(1.5当量),混合物在室温下搅拌24h,通过短硅胶层过滤,用CH2Cl2洗涤,有机层用MgSO4干燥、过滤、减压蒸发。通过硅胶柱色谱法纯化粗混合物,得到硅烷醇产物。
按照方法E制备,产物2a为无色液体(Rf=0.3,石油醚/乙酸乙酯=10∶1),产率为94%(722mg)。表征数据:1H NMR(400MHz,CDCl3)δ7.60-7.58(m,2H),7.39-7.37(m,3H),1.98(s,1H),0.40(s,6H)。13C NMR(101MHz,CDCl3)δ139.27,133.18,129.77,128.04,0.11。HRMS(ESI,m/z)精确质量计算C8HHOSi[M-H-]:151.0585,实测值:151.0575。
按照方法D、E制备,产物2b为无色液体(Rf=0.2,石油醚/乙酸乙酯=10∶1),两步收率为50%(903mg)。1H NMR(600MHz,CDCl3)δ7.51(d,J=8.4Hz,2H),6.92(d,J=7.8Hz,2H),3.81(s,3H),2.18(s,1H),0.37(s,6H)。3C NMR(151MHz,CDCl3)δ161.00,134.77,130.32,113.77,55.20,0.23。HRMS(ESI,m/z)精确质量计算C9H13O2Si[M-H-]:181.0690,实测值:181.0681。
按照方法D、E制备,产物2c为无色液体(Rf=0.2,石油醚/乙酸乙酯=20∶1),两步收率为30%(568mg)。表征数据:1H NMR(600MHz,CDCl3)δ7.50(d,J=7.8Hz,2H),7.35(d,J=7.2Hz,2H),2.11(s,1H),0.38(s,6H)。13C NMR(101MHz,CDCl3)δ137.50,136.07,134.59,128.27,0.16。HRMS(ESI,m/z)精确质量计算C8H10ClOSi[M-H-]:185.0195,实测值:185.0188。
按照方法D、E制备,产物2d为无色液体(Rf=0.2,石油醚/乙酸乙酯=20∶1),两步收率为44%(752mg)。表征数据:1H NMR(400MHz,CDCl3)δ7.53-7.45(m,1H),7.42-7.33(m,1H),7.18-7.12(m,1H),7.03-6.97(m,1H),2.05(s,1H),0.45(s,6H)。13C NMR(151MHz,CDCl3)δ167.03(d,JCF=241.4Hz),135.20(d,JCF=11.0Hz),131.81(d,JCF=8.4Hz),125.73(d,JCF=29.8Hz),123.93(d,JCF=2.8Hz),114.81(d,JCF=25.7Hz),1.44。19F NMR(565MHz,CDCl3)δ-101.15。HRMS(ESI,m/z)精确质量计算C8H12FOSi[M+H+]:171.0636,实测值:171.0627。
按照方法E制备,产物2e为无色液体(Rf=0.3,石油醚/乙酸乙酯=10∶1),收率为53%(565mg)。表征数据:1H NMR(400MHz,CDCl3)δ7.60-7.58(m,4H),7.40-7.34(m,6H),2.48(s,1H),0.65(s,3H)。13C NMR(151MHz,CDCl3)δ137.21,134.10,130.02,128.05,-1.13。HRMS(ESI,m/z)精确质量计算C13H13OSi[M-H-]:213.0741,实测值:213.0736。
根据参考文献【Angew.Chem.Int.Ed.2018,57,11952-11956.】制备2f。用氩气吹扫KOH(1.12g,20.0mmol)的H2O/甲醇(20mL,1/4,v/v)溶液,然后加入用氩气吹扫的叔丁基氯二苯基硅烷(5.0g,18.2mmol)的Et2O(30mL)溶液,所得混合物在室温下搅拌24h。分离水层,并用Et2O萃取,将合并的醚用MgSO4干燥并减压蒸发,得到澄清的油状物,静置后为白色固体,为叔丁基二苯基硅烷醇(1.54g,33%收率)。表征数据:1H NMR(400MHz,CDCl3)δ7.71(dd,J=7.0,0.7Hz,4H),7.41-7.35(m,6H),2.17(s,1H),1.07(s,9H)。13C NMR(101MHz,CDCl3)δ135.31,134.95,129.80,127.87,26.70,19.15。
根据参考文献【ACS Appl.Mater.Interfaces.2012,4,5813-5820.】制备2g。向冰浴冷却的NaH(60%矿物油,600mg,25mmol)的DMF(15mL)悬浮液中加入吩噻嗪(2.0g,10.0mmol)和2-溴乙醇(0.71ml,10.0mmol),悬浮液在室温、氮气下搅拌5h。混合物冷却至室温并加入盐水,用二氯甲烷收集有机相,并用Na2SO4干燥,蒸发溶剂后,粗化合物通过硅胶柱色谱法纯化,得到所需产物(1.12g,46%收率)。表征数据:1H NMR(400MHz,CDCl3):δ7.19-7.14(m,4H),6.97-6.89(m,4H),4.09(t,J=5.2Hz,2H),3.88(t,J=5.2Hz,2H),2.20(s,1H)。13CNMR(101MHz,CDCl3)δ145.19,127.85,127.51,126.30,123.14,115.98,58.80,49.68。
根据参考文献【Langmuir.2008,24,5140-5145.】制备2h。在0℃、氩气保护下,向1,6-二溴芘(1.8g,5.0mmol,在20mL 3∶1苯/醚溶液)中滴加nBuLi(2.5M己烷溶液,2.2当量,8.8mL),黄色混合物在60℃下回流2.0h,将混合物冷却至室温,并加入1.7g在10mL乙醚中的对甲醛,所得溶液加热至回流3.0h,然后冷却至室温,过滤除去浅橙色固体,用水和稀盐酸洗涤固体,真空下干燥(832mg,63%产率)。表征数据:1H NMR(600 MHz,DMSO-d6)δ8.34(d,J=9.6Hz,2H),8.27(d,J=7.8Hz,2H),8.19(d,J=9.0Hz,2H),8.14(d,J=7.8Hz,2H),5.25(s,4H)。13C NMR(151MHz,DMSO-d6)δ135.96,129.70,127.89,127.30,125.54,124.64,124.15,122.87,61.41。
实施例3
二氢硅烷与硅烷醇的反应条件筛选:
在Rh催化剂存在下,叔丁基(4-甲氧基苯基)硅烷1a与二甲基(苯基)硅烷醇2a进行分子间脱氢Si-O偶联反应,在室温、甲苯溶剂中,尝试了几种手性二膦配体,使用[Rh(cod)Cl]2(1mol%)作为催化剂和Josiphos L1(2.2mol%)作为手性配体,成功得到硅氧烷产物3a,产率为36%,对映体控制良好(ee为74%),其他具有不同电子特性的Josiphos型配体(L2和L3)也是可行的配体。
使用磷原子的取代基互换的Josiphos配体L4,收率和对映选择性显著提升(68%收率、97%ee)。对手性配体的进一步筛选发现,BINAP L5和Segphos L6也对该反应有效。
使用L4配体,常见的溶剂DCE(1,2-二氯乙烷)和1,4-二氧六环会使收率有所下降。
反应条件:在氩气氛下,于2.0mL溶剂中,1a(0.24mmol)、2a(0.2mmol)、[Rh(cod)Cl]2(1mol%)、配体(2.2mol%),反应12小时;使用CH2Br2作为内标,通过1H NMR测定产率;ee值通过手性HPLC测定。
产物为无色油状物(Rf=0.5,石油醚)。用Daicel Chiralpak OD-3色谱柱分析(正己烷,0.6mL/min),λ=210nm,温度=28℃,tr(minor)=9.3min,tr(maior)=9.7min。表征数据:[α]D 23.0=-28.0(c=1.0,CHCl3)。1H NMR(600MHz,CDCl3)δ7.55(d,J=6.6Hz,2H),7.47(d,J=7.8Hz,2H),7.37-7.33(m,3H),6.89(d,J=8.4Hz,2H),4.77(s,1H),3.81(s,3H),0.90(s,9H),0.35(s,6H)。13C NMR(151MHz,CDCl3)δ161.06,139.59,135.75,133.19,129.45,127.85,126.46,113.50,55.12,25.53,18.37,0.70。HRMS(ESI,m/z)精确质量计算C19H29O2Si2[M+H+]:345.1701,实测值:345.1701。
在获得最佳反应条件后,用该方法构建硅中心手性的硅氧烷,带有不同取代基(给电子的甲氧基、吗啉基,吸电子的氟)的苯环、萘环,均与二甲基(苯基)硅烷醇2a反应,以中等至良好的收率(54~98%)、优异的对映选择性(96~98%ee),得到相应产物。接着拓展硅烷醇的适用范围,二甲基苯基硅烷醇的苯环上连有甲氧基、氯和氟的底物均有良好的耐受性,以89~97%ee得到产物。甲基二苯基硅烷醇、叔丁基二苯基硅烷醇和三甲基硅烷醇也是可行的底物,以56~75%的收率得到了产物,对映选择性(93~97%)没有下降。将硅烷二醇与二氢硅烷进行双偶联,可以构建两个硅手性中心的硅烷。将tBu替换为甲基、异丙基、环己基或1-萘基,顺利得到相应的产物,ee为63~88%。
步骤F:在手套箱中,向10mL小瓶中依次添加[Rh(cod)Cl]2(1.0mg,1mol%)、L4(2.4mg,2.2mol%)、甲苯(2mL)、二氢硅烷底物(0.24mmol,1.2当量)、硅烷醇底物(0.2mmol,1.0当量)。将反应管盖好,然后从手套箱中移出并在室温下搅拌过夜。反应完成后,反应混合物通过短硅胶层过滤并减压蒸发,通过制备型TLC纯化,得到目标产物。通过手性HPLC分析确定对映体过量,在相同条件下与(±)-BINAP或(±)-L4反应,获得相应的外消旋产物作为参考。
步骤G:手性硅烷产物的氧化。向甲基三氧化铼(MTO,10mol%)的二氯甲烷(0.2M)溶液中添加尿素/过氧化氢混合物(UHP,1.0当量),所得混合物搅拌10min,然后添加硅烷底物(1.0当量)。在环境温度下搅拌过夜后,混合物通过短硅胶层过滤,浓缩后,粗产物通过制备TLC纯化,得到目标产物。
实施例4
按照方法F制备,产物为无色油状物(Rf=0.4,石油醚/乙酸乙酯=20∶1),收率为98%(79mg),97%ee。用Daicel Chiralpak OD-3色谱柱分析(正己烷,0.6mL/min),λ=220nm,温度=28℃,tr(minor)=15.6min,tr(major)=17.9min。表征数据:1H NMR(400MHz,CDCl3)δ7.56-7.54(m,2H),7.44(d,J=8.4Hz,2H),7.36-7.32(m,3H),6.88(d,J=8.8Hz,2H),4.77(s,1H),3.85(t,J=4.8Hz,4H),3.19(t,J=4.8Hz,4H),0.91(s,9H),0.35(s,6H)。13CNMR(101MHz,CDCl3)δ152.22,139.66,135.44,133.18,129.40,127.82,124.96,114.43,67.01,48.60,25.56,18.43,0.73。HRMS(ESI,m/z)精确质量计算C22H34NO2Si2[M+H+]:400.2123,实测值:400.2120。
实施例5
按照方法F制备,产物为无色油状物(Rf=0.4,石油醚),收率为54%(36mg),氧化后,通过HPLC确定96%ee(Si-OH产物)。表征数据:1H NMR(600MHz,CDCl3)δ7.54-7.49(m,4H),7.37-7.33(m,3H),7.04(t,J=9.0Hz,2H),4.79(s,1H),0.90(s,9H),0.36(s,6H)。13CNMR(151MHz,CDCl3)δ164.30(d,JCF=249.0Hz),139.30,136.17(d,JCF=7.4Hz),133.15,131.00(d,JCF=4.0Hz),129.57,127.90,115.00(d,JCF=20.0Hz),25.43,18.28,0.63,0.61。19FNMR(565MHz,CDCl3)δ-110.78。HRMS(ESI,m/z)精确质量计算C18H26FOSi2[M+H+]:333.1501,实测值:333.1501。
按照方法G制备,产物为无色油状物(Rf=0.2,石油醚/乙酸乙酯=20∶1),产率为69%(22mg),96%ee。用Daicel Chiralpak AD-3色谱柱分析(正己烷/异丙醇=99.5∶0.5,1.0mL/min),λ=220nm,温度=28℃,tr(minor)=18.6min,tr(major)=20.5min。表征数据:[α]D 20.8=-16.7(c=1.0,CHCl3)。1H NMR(400MHz,CDCl3)δ7.60-7.55(m,4H),7.40-7.32(m,3H),7.08-7.01(m,2H),2.28(s,1H),0.92(s,9H),0.41(s,3H),0.40(s,3H)。13C NMR(101MHz,CDCl3)δ164.35(d,JCF=249.8Hz),139.35,136.81(d,JCF=7.5Hz),133.14,130.25(d,JCF=3.7Hz),129.67,128.00,114.90(d,JCF=19.7Hz),25.83,18.47,0.90,0.85。19FNMR(376MHz,CDCl3)δ-110.68。HRMS(ESI,m/z)精确质量计算C18H26FO2Si2[M+H+]:349.1450,实测值:349.1448。
实施例6
按照方法F制备,产物为无色油状物(Rf=0.6,石油醚),收率为69%(43mg),氧化后,通过HPLC确定98%ee(Si-OH产物)。表征数据:1H NMR (400 MHz,CDCl3)δ7.56-7.53(m,4H),7.39-7.32(m,6H),4.80(s,1H),0.92(s,9H),0.36(s,6H)。13C NMR(101MHz,CDCl3)δ139.49,135.44,134.23,133.19,129.84,129.49,127.87,127.73,25.54,18.32,0.68。HRMS(ESI,m/z)精确质量计算C18H27OSi2[M+H+]:315.1595,实测值:315.1592。
按照方法G制备,产物为无色油状物(Rf=0.3,石油醚/乙酸乙酯=20∶1),产率为73%(35mg),98%ee。用Daicel Chiralpak OD-3色谱柱分析(正己烷/异丙醇=99.5∶0.5,1.0mL/min),λ=220nm,温度=28℃,tr(major)=16.2min,tr(minor)=17.1min。表征数据:[α]D 23.2=-28.1(c=1.0,CHCl3).1H NMR(400MHz,CDCl3)δ7.62-7.57(m,4H),7.41-7.31(m,6H),2.31(s,1H),0.93(s,9H),0.41(s,3H),0.40(s,3H).13C NMR(101MHz,CDCl3)δ139.52,134.77,134.61,133.17,129.94,129.58,127.96,127.70,25.89,18.49,0.97,0.92.HRMS(ESI,m/z)精确质量计算C18H27O2Si2[M+H+]:331.1544,实测值:331.1556。
实施例7
按照方法F制备,产物为无色油状物(Rf=0.3,石油醚),收率为60%(43.5mg),氧化后,通过HPLC确定96%ee(Si-OH产物)。表征数据:1H NMR(600MHz,CDCl3)δ8.23(d,J=8.4Hz,1H),7.88(d,J=7.8Hz,1H),7.83(d,J=7.8Hz,1H),7.75(d,J=7.2,1H),7.57-7.55(m,2H),7.46-7.43(m,3H),7.35-7.32(m,3H),5.23(s,1H),0.95(s,9H),0.37(s,6H)。13CNMR(151MHz,CDCl3)δ139.32,137.34,134.71,133.63,133.38,133.23,130.42,129.51,128.89,128.76,127.86,125.75,125.62,124.97,26.27,19.22,0.54,0.53。
按照方法G制备,产物为无色油状物(Rf=0.2,石油醚/乙酸乙酯=20∶1),产率为63%(24mg),96%ee。用Daicel Chiralpak OD-3色谱柱分析(正己烷/异丙醇=99.0∶1.0,1.0mL/min),λ=220nm,温度=28℃,tr(major)=6.5min,tr(minor)=6.8min。表征数据:[α]D 22.8=-26.4(c=1.0,CHCl3)。1H NMR(400MHz,CDCl3)δ8.47-8.44(m,1H),7.90-7.82(m,3H),7.59(dd,J=7.6,1.6Hz,2H),7.47-7.41(m,3H),7.37-7.30(m,3H),2.44(s,1H),0.95(s,9H),0.44(s,3H),0.42(s,3H)。13C NMR(101 MHz,CDCl3)δ139.40,137.36,135.94,133.51,133.22,132.90,130.77,129.71,129.65,128.76,128.00,125.83,125.52,124.90,26.38,19.21,0.88,0.78。HRMS(ESI,m/z)精确质量计算C22H28NaO2Si2[M+Na+]:403.1520,实测值:403.1529。
实施例8
按照方法F制备,产物为无色油状物(Rf=0.4,石油醚),收率为52%(36mg),氧化后,通过HPLC确定89%ee(Si-OH产物)。表征数据:1H NMR(600 MHz,CDCl3)δ7.54-7.53(m,2H),7.49-7.47(m,2H),7.40-7.37(m,1H),7.35-7.32(m,2H),6.90-6.88(m,2H),4.79(s,1H),3.80(s,3H),0.91(s,9H),0.34(s,6H)。13C NMR(151MHz,CDCl3)δ160.76,135.53,134.74,134.22,130.61,129.80,127.71,113.58,55.15,25.54,18.31,0.79。HRMS(ESI,m/z)精确质量计算C19H29O2Si2[M+H+]:345.1701,实测值:345.1700。
按照方法G制备,产物为无色油状物(Rf=0.2,石油醚/乙酸乙酯=20∶1),产率为42%(15mg),89%ee。用Daicel Chiralpak OD-3色谱柱分析(正己烷/异丙醇=99.0∶1.0,1.0mL/min),λ=220nm,温度=28℃,tr(major)=5.7min,tr(minor)=6.4min。表征数据:[α]D 22.3=-13.6(c=1.0,CHCl3)。1H NMR(400MHz,CDCl3)δ7.62-7.59(m,2H),7.53-7.49(m,2H),7.40-7.32(m,3H),6.91-6.88(m,2H),3.81(s,3H),2.21(s,1H),0.93(s,9H),0.39(s,3H),0.38(s,3H)。13C NMR(101MHz,CDCl3)δ160.79,134.77,134.74,130.62,129.91,127.69,113.66,55.16,25.88,18.49,1.08,1.02。HRMS(ESI,m/z)精确质量计算C19H29O3Si2[M+H+]:361.1650,实测值:361.1649。
实施例9
按照方法F制备,产物为无色油状物(Rf=0.5,石油醚),收率为75%(57mg),97%ee。用Daicel Chiralpak OD-3色谱柱分析(正己烷,0.6mL/min),λ=220nm,温度=28℃,tr(minor)=8.8min,tr(major)=9.1min。表征数据:[α]D 23.0=-30.2(c=1.0,CHCl3)。1H NMR(400MHz,CDCl3)δ7.45(d,J=8.4Hz,4H),7.31(d,J=8.0Hz,2H),6.91-6.88(m,2H),4.76(s,1H),3.81(s,3H),0.90(s,9H),0.34(s,6H)。13C NMR(101MHz,CDCl3)δ161.14,137.83,137.27,135.71,134.59,128.11,126.21,113.56,55.11,25.51,18.35,0.65,0.63.HRMS(ESI,m/z)精确质量计算C19H28ClO2Si2[M+H+]:379.1311,实测值:379.1314。
实施例10
按照方法F制备,产物为无色油状物(Rf=0.4,石油醚),收率为55%(40mg),氧化后,通过HPLC确定95%ee(Si-OH产物)。表征数据:H NMR(400MHz,CDCl3)δ7.39-7.35(m,3H),7.27-7.21(m,1H),7.00(t,J=7.2Hz,1H),6.88-6.78(m,3H),4.69(s,1H),3.70(s,3H),0.81(s,9H),0.29(s,6H)。13C NMR(101MHz,CDCl3)δ166.95(d,JCF=242.3Hz),161.10,135.74,135.19(d,JCF=11.1Hz),131.81(d,J=11.2Hz),126.32,124.52(d,JCF=29.7Hz),123.92(d,JCF=2.9Hz),114.82(d,JCF=25.4Hz),113.53,55.11,25.52,18.38,1.30,1.24。19FNMR(376MHz,CDCl3)δ-101.04。HRMS(ESI,m/z)精确质量计算C19H28FO2Si2[M+H+]:363.1606,实测值:363.1617。
按照方法G制备,产物为无色油状物(Rf=0.2,石油醚/乙酸乙酯=20∶1),产率为93%(35mg),95%ee。用Daicel Chiralpak OD-3色谱柱分析(正己烷/异丙醇=99.0∶1.0,1.0mL/min),λ=220nm,温度=28℃,t(major)=6.2min,t(minor)=6.9min。表征数据:[α]D 22.0=-12.8(c=1.0,CHCl3)。1H NMR(400MHz,CDCl3)δ7.57-7.51(m,3H),7.37-7.36(m,1H),7.14-7.10(m,1H),6.98(t,J=8.2Hz,1H),6.91-6.88(m,2H),3.82(s,3H),2.34(s,1H),0.94(s,9H),0.46(d,J=0.8Hz,3H),0.45(d,J=0.8Hz,3H)。13C NMR(101MHz,CDCl3)δ167.04(d,JCF=242.1Hz),161.12,136.30,135.18(d,JCF=11.1Hz),131.91(d,JCF=8.5Hz),125.54,125.53(d,JCF=29.4Hz),124.02(d,JCF=2.9Hz),114.89(d,JCF=25.4Hz),113.44,55.12,25.89,18.56,1.56,1.53。19F NMR(376MHz,CDCl3)δ-101.06。HRMS(ESI,m/z)精确质量计算C19H28FO3Si2[M+H+]:379.1556,实测值:379.1557。
实施例11
按照方法F制备,产物为无色油状物(Rf=0.6,石油醚),收率为65%(49mg),97%ee。用Daicel Chiralpak OD-3色谱柱分析(正己烷,1.0mL/min),λ=220nm,温度=28℃,tr(major)=4.9min,tr(minor)=5.1min。表征数据:[α]D 20.9=-21.4(c=1.0,CHCl3)。1H NMR(600MHz,CDCl3)δ7.55-7.51(m,6H),7.37(t,J=7.2Hz,3H),7.33-7.30(m,6H),4.86(s,1H),0.91(s,9H),0.62(s,3H)。13C NMR(151MHz,CDCl3)δ137.59,137.54,135.11,134.32,134.13,129.89,129.76,127.88,127.72,25.57,18.46,-0.73。HRMS(ESI,m/z)精确质量计算C23H29OSi2[M+H+]:377.1751,实测值:377.1756。
实施例12
按照方法F制备,产物为无色油状物(Rf=0.4,石油醚),收率为56%(50mg),93%ee。用Daicel Chiralpak OD-3色谱柱分析(正己烷,0.6mL/min),λ=220nm,温度=28℃,tr(minor)=9.8min,tr(major)=10.1min。表征数据:[α]D 23.3=-6.8(c=1.0,CHCl3)。1H NMR(400MHz,CDCl3)δ7.64-7.60(m,4H),7.45-7.43(m,2H),7.31-7.29(m,2H),7.31-7.29(m,4H),6.83(d,J=8.2Hz,2H),4.93(s,1H),3.79(s,3H),1.03(s,9H),0.90(s,9H)。13C NMR(101MHz,CDCl3)δ161.00,136.00,135.48,135.43,135.42,129.51,127.57,127.54,126.25,113.42,55.08,26.99,25.80,19.73,18.83。HRMS(ESI,m/z)精确质量计算C27H37O2Si2[M+H+]:449.2327,实测值:449.2328。
实施例13
按照方法F制备,产物为无色油状物(Rf=0.6,石油醚),收率为75%(42mg),氧化后,通过HPLC确定97%ee(Si-OH产物)。表征数据:1H NMR(400MHz,CDCl3)δ7.48(d,J=8.2Hz,2H),6.91(d,J=8.2Hz,2H),4.71(s,1H),3.82(s,3H),0.90(s,9H),0.11(s,9H)。13CNMR(101MHz,CDCl3)δ161.01,135.65,126.84,113.49,55.11,25.50,18.24,1.78。HRMS(ESI,m/z)精确质量计算C14H27O2Si2[M+H+]:283.1544,实测值:283.1548。
按照方法G制备,产物为无色油状物(Rf=0.2,石油醚/乙酸乙酯=20∶1),产率为41%(16mg),97%ee。用Daicel Chiralpak OD-3色谱柱分析(正己烷/异丙醇=99.0∶1.0,1.0mL/min),λ=220nm,温度=28℃,tr(major)=4.7min,tr(minor)=5.3min。表征数据:[α]D 22.9=-43.0(c=1.0,CHCl3)。1H NMR(400MHz,CDCl3)δ7.57-7.54(m,2H),6.93-6.90(m,2H),3.82(s,3H),2.26(s,1H),0.93(s,9H),0.16(s,9H)。13C NMR(101MHz,CDCl3)δ161.06,136.28,126.03,113.42,55.12,25.91,18.47,2.11。HRMS(ESI,m/z)精确质量计算C14H27O3Si2[M+H+]:299.1493,实测值:299.1496。
实施例14
按照方法F制备,产物为无色油状物(Rf=0.6,石油醚/乙酸乙酯=20∶1),收率为59%(64mg),氧化后,通过HPLC确定>99%ee、98∶2dr(Si-OH产物)。表征数据:1H NMR(400MHz,CDCl3)δ7.56-7.54(m,4H),7.45-7.43(m,4H),7.38-7.32(m,4H),7.29-7.22(m,8H),4.86(s,2H),0.86(s,18H)。13C NMR(101 MHz,CDCl3)δ135.14,134.66,134.57,134.37,130.11,129.84,127.75,127.64,25.53,18.46。
按照方法G制备,产物为无色油状物(Rf=0.2,石油醚/乙酸乙酯=20∶1),产率为57%(33mg),>99%ee、98∶2dr。用Daicel Chiralpak OD-3色谱柱分析(正己烷/异丙醇=99.5∶0.5,1.0mL/min),λ=220nm,温度=28℃,tr(major)=19.0min,tr(meso)=21.5min,tr(minor)=27.2min。表征数据:[α]D 23.3=17.1(c=1.0,CHCl3)。1H NMR(600MHz,CDCl3)δ7.68-7.67(m,4H),7.46-7.44(m,4H),7.42-7.38(m,4H),7.36-7.33(m,4H),7.29-7.26(m,4H),2.82(s,2H),0.80(s,18H)。13C NMR(101MHz,CDCl3)δ135.20,134.89,134.69,134.60,134.56,134.06,133.75,130.31,130.25,130.15,129.90,127.95,127.89,127.79,127.72,127.59,25.81,25.66,18.51,18.38。HRMS(APCI,m/z)精确质量计算C32H39O4Si3[M-H-]:571.2164,实测值:571.2162。
实施例15
按照方法F制备,产物为无色油状物(Rf=0.6,石油醚),收率为48%(26mg),63%ee。用Daicel Chiralpak OJ-3色谱柱分析(正己烷,1.0mL/min),λ=220nm,温度=28℃,tr(major)=5.5min,tr(minor)=7.1min。表征数据:[α]D 22.4=-1.6(c=1.0,CHCl3)。1H NMR(400MHz,CDCl3)δ7.57-7.53(m,4H),7.40-7.34(m,6H),5.14(q,J=2.8Hz,1H),0.41(d,J=2.8Hz,3H),0.35(s,6H)。13C NMR(101MHz,CDCl3)δ139.48,137.72,133.53,133.15,129.93,129.52,128.01,127.90,0.71,0.67,-0.19。HRMS(ESI,m/z)精确质量计算C15H21OSi2[M+H+]:273.1125,实测值:273.1123。
实施例16
按照方法F制备,产物为无色油状物(Rf=0.5,石油醚),收率为50%(30mg),氧化后,通过HPLC确定72%ee(Si-OH产物)。1H NMR(400MHz,CDCl3)δ7.56-7.52(m,4H),7.39-7.33(m,6H),4.89(d,J=2.0Hz,1H),1.27-0.86(m,7H),0.36(s,6H)。13C NMR(101MHz,CDCl3)δ139.50,135.94,133.99,133.17,129.86,129.49,127.88,16.67,14.50,0.67。HRMS(ESI,m/z)精确质量计算C17H25OSi2[M+H+]:301.1438,实测值:301.1453。
按照方法G制备,产物为无色油状物(Rf=0.3,石油醚/乙酸乙酯=20∶1),产率为44%(14mg),72%ee。用Daicel Chiralpak OD-3色谱柱分析(正己烷/异丙醇=99.0∶1.0,1.0mL/min),λ=220nm,温度=28℃,tr(minor)=6.1min,tr(major)=6.5min。表征数据:[α]D 22.8=-8.3(c=1.0,CHCl3)。1H NMR(600MHz,CDCl3)δ7.60-7.58(m,4H),7.40-7.34(m,6H),2.25(s,1H),1.04-0.98(m,7H),0.41(s,3H),0.40(s,3H)。13C NMR(151MHz,CDCl3)δ139.53,135.32,134.23,133.16,130.02,129.58,127.96,127.86,16.89,16.82,14.21,0.94,0.90。HRMS(ESI,m/z)精确质量计算C17H25O2Si2[M+H+]:317.1388,实测值:317.1382。
实施例17
按照方法F制备,产物为无色油状物(Rf=0.6,石油醚),收率为51%(35mg),氧化后,通过HPLC确定70%ee(Si-OH产物)。表征数据:1H NMR(400MHz,CDCl3)δ7.56-7.51(m,4H),7.38-7.32(m,6H),4.88(d,J=1.6Hz,1H),1.76-1.66(m,5H),1.19-1.13(m,5H),0.94-0.92(m,1H),0.36(s,3H),0.35(s,3H)。13C NMR(101MHz,CDCl3)δ139.52,136.04,133.97,133.18,129.80,129.47,127.85,27.71,26.91,26.63,26.56,26.34,0.69。HRMS(ESI,m/z)精确质量计算C20H29O5i2[M+H+]:341.1751,实测值:341.1747。
按照方法G制备,产物为无色油状物(Rf=0.3,石油醚/乙酸乙酯=20∶1),产率为66%(24mg),70%ee。用Daicel Chiralpak AD-3色谱柱分析(正己烷/异丙醇=99.5∶0.5,1.0mL/min),λ=220nm,温度=28℃,t(major)=14.1min,t(minor)=14.8min。表征数据:[α]D 22.8=-4.8(c=1.0,CHCl3)。1H NMR(600MHz,CDCl3)δ7.59-7.57(m,4H),7.41-7.33(m,6H),2.26(s,1H),1.74-1.67(m,5H),1.17-1.16(m,5H),0.89-0.85(m,1H),0.41(s,3H),0.39(s,3H)。13C NMR(151 MHz,CDCl3)δ139.56,135.56,134.21,133.18,129.98,129.57,127.95,127.83,27.79,26.88,26.67,26.63,26.21,0.97,0.94。HRMS(ESI,m/z)精确质量计算C20H28KO2Si2[M+K+]:395.1259,实测值:395.1253。
实施例18
按照方法F制备,产物为无色油状物(Rf=0.5,石油醚),收率为71%(55mg),88%ee。用Daicel Chiralpak OD-3色谱柱分析(正己烷,1.0mL/min),λ=220nm,温度=28℃,tr(major)=9.8min,tr(minor)=10.7min。表征数据:[α]D 22.3=-2.8(c=1.0,CHCl3)。1H NMR(600MHz,CDCl3)δ8.06(d,J=8.4Hz,1H),7.91(d,J=7.8Hz,1H),7.85-7.82(m,2H),7.58(d,J=7.2Hz,2H),7.52(d,J=6.6Hz,2H),7.48-7.43(m,2H),7.38-7.28(m,7H),5.88(s,1H),0.35(s,3H),0.34(s,3H)。13C NMR(151MHz,CDCl3)δ139.05,136.86,136.12,135.09,134.32,133.65,133.33,133.23,131.02,130.15,129.56,128.86,128.17,128.09,127.86,126.18,125.81,125.26,0.55。
实施例19
将本发明的方法扩展到二氢硅烷与醇的偶联反应,条件筛选过程为:在手套箱中,向10mL小瓶中依次添加[Rh(cod)Cl]2(1.0mg,1mol%)、配体(2.4mg,2.2mol%)、溶剂(2mL)、叔丁基(苯基)硅烷(39.4mg,0.24mmol,1.2当量)、BnOH(21.6mg,0.2mmol,1.0当量)。将反应管盖好,然后从手套箱中取出并在室温下搅拌12h。反应完成后,将反应混合物通过短硅胶层过滤并减压蒸发,粗残余物溶于0.6mL氘代氯仿中,用CH2Br2作为内标通过1H NMR分析确定产率,用Daicel Chiralpak OD-3柱进行HPLC分析(正己烷,0.6mL/min)确定产物的ee值,结果如下表所示:
产物为白色固体(Rf=0.4,石油醚),收率为78%(42mg),99%ee。用DaicelChiralpak OD-3色谱柱分析(正己烷,0.6mL/min),λ=220nm,温度=28℃,tr(maior)=8.4min,tr(minor)=9.3min。表征数据:[α]D 19.1=-48.2(1.0,CHCl3)。1H NMR(600MHz,CDCl3)δ7.60-7.58(m,2H),7.44-7.41(m,1H),7.39-7.36(m,2H),7.32(d,J=4.2Hz,4H),7.26-7.24(m,1H),4.81-4.76(m,3H),1.00(s,9H)。13C NMR(151MHz,CDCl3)δ140.71,134.71,133.63,130.19,128.37,127.95,127.23,126.43,66.90,25.82,18.26。HRMS(ESI,m/z)精确质量计算C17H23OSi[M+H+]:271.1513,实测值:271.1519。
在获得最佳反应条件后,用该方法构建硅中心手性的硅醚,多种不同取代基的醇均可作为底物。带有给电子或吸电子取代基(例如甲基、甲氧基、溴、三氟甲基)的苯甲醇底物以64~88%的产率、92~99%ee得到相应的硅醚产物。将苯环换成萘、呋喃、噻吩等杂环也是可行的。有位阻的仲醇和叔醇也能顺利进行,以优异对映选择性(98~99%ee)获得目标产物。除苯甲醇外,含不同取代基的脂族醇也是合适的底物,收率66~83%,ee为96~97%。为了进一步证明本发明方法的实用性,使用了几种含有生物活性分子、药物或材料构造单元(吩噻嗪、D-核呋喃糖苷、β-雌二醇、匹伐他汀)的底物。不管这些底物的官能团和分子结构如何复杂,都以良好的收率获得具有优良立体选择性的硅手性硅醚产物。此外,通过1,4-苯二甲基甲醇与二氢硅烷之间反应获得双硅立体中心的硅醚,收率为52%,对映选择性大于99%ee。
方法H:在手套箱中,向10mL小瓶中依次添加[Rh(cod)Cl]2(1.0mg,1mol%)、L4(2.4mg,2.2mol%)、甲苯(2mL)、二氢硅烷底物(0.24mmol,1.2当量)、醇底物(0.2mmol,1.0当量)。将反应管盖好,然后从手套箱中移出并在室温下搅拌过夜。反应完成后,反应混合物通过短硅胶层过滤并减压蒸发,然后通过制备型TLC纯化,得到目标产物。通过手性HPLC分析确定ee值。在相同的条件下与(±)-BINAP或(±)-Josiphos反应获得相应的外消旋样品作为参考。
实施例20
按照方法H制备,产物为无色油状物(Rf=0.4,石油醚),收率为88%(50mg),98%ee。用Daicel Chiralpak OJ-3色谱柱分析(正己烷,1.0mL/min),λ=220nm,温度=28℃,tr(major)=7.5min,tr(minor)=10.4min。表征数据:[α]D 23.1=-38.2(c=1.0,CHCl3)。1H NMR(600MHz,CDCl3)δ7.59(dd,J=7.8,1.2Hz,2H),7.43-7.40(m,1H),7.38-7.36(m,2H),7.20(d,J=7.8Hz,2H),7.13(d,J=7.8Hz,2H),4.80-4.71(m,3H),2.33(s,3H),0.98(s,9H)。13CNMR(151MHz,CDCl3)δ137.68,136.84,134.72,133.72,130.14,129.05,127.92,126.58,66.84,25.82,21.28,18.24。
实施例21
按照方法H制备,产物为无色油状物(Rf=0.3,石油醚),收率为76%(48mg),92%ee。用Daicel Chiralpak OJ-3色谱柱分析(正己烷/异丙醇=99.0∶1.0,0.6mL/min),λ=220nm,温度=28℃,tr(minor)=10.9min,tr(major)=11.8min。表征数据:[α]D 22.4=-23.4(c=1.0,CHCl3)。1H NMR(400MHz,CDCl3)δ7.58-7.56(m,2H),7.44-7.36(m,3H),6.84(s,1H),6.74(s,2H),5.93(s,2H),4.73(s,1H),4.70-4.61(m,2H),0.98(s,9H)。13C NMR(101MHz,CDCl3)δ147.74,146.79,134.69,133.61,130.18,127.94,119.87,108.09,107.52,101.01,66.87,25.80,18.21。HRMS(ESI,m/z)精确质量计算C18H23O3Si[M+H+]:315.1411,实测值:315.1409。
实施例22
按照方法H制备,产物为无色油状物(Rf=0.4,石油醚),收率为66%(50mg),91%ee。用Daicel Chiralpak OD-3色谱柱分析(正己烷,1.0mL/min),λ=220nm,温度=28℃,tr(major)=10.9min,tr(minor)=19.1min。表征数据:[α]D 22.9=-23.5(c=1.0,CHCl3)。1HNMR(400MHz,CDCl3)δ7.51-7.48(m,2H),7.44(d,J=8.2Hz,2H),7.18(d,J=8.4Hz,2H),6.94-6.92(m,2H),4.73-4.66(m,3H),3.82(s,3H),0.98(s,9H)。13C NMR(101MHz,CDCl3)δ161.44,139.82,136.24,131.44,128.14,124.19,120.94,113.82,66.12,55.16,25.79,18.27。HRMS(ESI,m/z)精确质量计算C18H24BrO2Si[M+H+]:379.0723,实测值:379.0728。
实施例23
按照方法H制备,产物为无色油状物(Rf=0.3,石油醚),收率为64%(43mg),96%ee。用Daicel Chiralpak OD-3色谱柱分析(正己烷,0.6mL/min),λ=220nm,温度=28℃,tr(major)=8.3min,tr(minor)=8.7min。表征数据:[α]D 22.8=-32.9(c=1.0,CHCl3)。1H NMR(600MHz,CDCl3)δ7.59-7.57(m,4H),7.45-7.42(m,3H),7.38(t,J=7.2Hz,2H),4.85-4.80(m,2H),4.77(s,1H),1.01(s,9H)。13C NMR(151MHz,CDCl3)δ144.77,134.66,133.20,130.40,129.48(q,JCF=32.4Hz),128.07,126.41,125.35(q,JCF=3.3Hz),124.44(q,JCF=270.8,),66.22,25.77,18.27。19F NMR(565MHz,CDCl3)δ-62.38。
实施例24
按照方法H制备,产物为白色固体(Rf=0.4,石油醚),收率为80%(51mg),96%ee。用Daicel Chiralpak IB色谱柱分析(正己烷,0.6mL/min),λ=220nm,温度=28℃,tr(minor)=14.6min,tr(major)=15.0min。表征数据:[α]D 20.8=-23.7(c=1.0,CHCl3)。1HNMR(400MHz,CDCl3)δ7.82-7.76(m,4H),7.63-7.60(m,2H),7.48-7.36(m,6H),4.97-4.90(m,2H),4.80(s,1H),1.02(s,9H)。13C NMR(101MHz,CDCl3)δ138.16,134.74,134.25,133.61,133.47,132.92,130.23,128.07,128.03,127.97,127.82,126.11,125.74,124.96,67.11,25.85,18.30。HRMS(ESI,m/z)精确质量计算C21H25OSi[M+H+]:321.1669,实测值:321.1661。
实施例25
按照方法H制备,产物为无色油状物(Rf=0.4,石油醚),收率为62%(34mg),95%ee。用Daicel Chiralpak OD-3色谱柱分析(正己烷,0.6mL/min),λ=220nm,温度=28℃,tr(major)=9.9min,tr(minor)=10.8min。表征数据:[α]D 23.2=-52.8(c=1.0,CHCl3)。1H NMR(400MHz,CDCl3)δ7.60-7.58(m,2H),7.45-7.35(m,3H),7.23(dd,J=5.1,1.2Hz,1H),6.93-6.91(m,1H),6.88-6.87(m,1H),4.95-4.87(m,2H),4.74(s,1H),0.97(s,9H)。13C NMR(101MHz,CDCl3)δ144.12,134.72,133.42,130.25,127.96,126.63,125.04,124.58,62.42,25.73,18.15。HRMS(ESI,m/z)精确质量计算C15H21OSSi[M+H+]:277.1077,实测值:277.1076。
实施例26
按照方法H制备,产物为无色油状物(Rf=0.4,石油醚),收率为79%(41mg),95%ee。用Daicel Chiralpak OD-3色谱柱分析(正己烷,0.6mL/min),λ=220nm,温度=28℃,tr(minor)=9.5min,tr(major)=10.7min。表征数据:[α]D 21.3=-20.5(c=1.0,CHCl3)。1H NMR(400MHz,CDCl3)δ7.58-7.56(m,2H),7.42-7.34(m,4H),6.28(dd,J=3.1,1.9Hz,1H),6.19(d,J=2.9Hz,1H),4.72-4.65(m,3H),0.95(s,9H)。13C NMR(101MHz,CDCl3)δ153.67,142.38,134.68,133.57,130.13,127.88,110.27,107.96,59.86,25.73,18.17。HRMS(ESI,m/z)精确质量计算C15H21O2Si[M+H+]:261.1305,实测值:261.1308。
实施例27
按照方法H制备,产物为白色固体(Rf=0.3,石油醚),收率为98%(67mg),98%ee。用Daicel Chiralpak OD-3色谱柱分析(正己烷/异丙醇=99.0∶1.0,0.6mL/min),λ=220nm,温度=28℃,tr(minor)=6.9min,tr(major)=7.2min。表征数据:[α]D 22.8=-36.1(c=1.0,CHCl3)。1H NMR(400MHz,CDCl3)δ7.62-7.53(m,5H),7.41-7.30(m,6H),7.24-7.19(m,2H),5.73(s,1H),4.96(s,1H),0.99(s,9H)。13C NMR(101MHz,CDCl3)δ145.54,145.34,140.17,134.92,134.10,130.21,128.82,127.87,127.50,125.52,125.46,119.93,119.88,25.89,18.34。HRMS(APCI,m/z)精确质量计算C23H23OSi[M-H-]:343.1524,实测值:343.1524。
实施例28
按照方法H制备,产物为无色油状物(Rf=0.5,石油醚),收率为50%(30mg),99%ee。用Daicel Chiralpak OD-3色谱柱分析(正己烷,0.6mL/min),λ=220nm,温度=28℃,tr(major)=6.5min,tr(minor)=7.3min。表征数据:[α]D 22.8=-8.8(c=1.0,CHCl3)。1H NMR(600MHz,CDCl3)δ7.58(d,J=7.2Hz,2H),7.51(d,J=7.8Hz,2H),7.38-7.31(m,5H),7.23(t,J=7.2Hz,1H),4.86(s,1H),1.60(s,3H),1.50(s,3H),0.98(s,9H)。13C NMR(151MHz,CDCl3)δ149.80,136.17,134.50,129.72,128.08,127.68,126.47,124.71,75.97,32.07,31.75,25.94,18.01。HRMS(ESI,m/z)精确质量计算C19H26NaOSi[M+Na+]:321.1645,实测值:321.1661。
实施例29
按照方法H制备,产物为无色油状物(Rf=0.4,石油醚),收率为67%(42mg),96%ee。用Daicel Chiralpak OJ-3色谱柱分析(正己烷/异丙醇=99.0∶1.0,1.0mL/min),λ=220nm,温度=28℃,tr(major)=6.1min,tr(minor)=8.4min。表征数据:[α]D 22.7=-40.0(c=1.0,CHCl3)。1H NMR(400MHz,CDCl3)δ7.50-7.48(m,2H),7.40-7.32(m,3H),7.09(d,J=8.8Hz,2H),6.80(d,J=8.8Hz,2H),4.63(s,1H),3.84(t,J=8.8Hz,2H),3.78(s,3H),2.81(t,J=8.8Hz,2H),0.93(s,9H)。13C NMR(101MHz,CDCl3)δ158.20,134.65,133.95,131.14,130.22,130.03,127.83,113.80,66.57,55.40,38.28,25.77,18.13。HRMS(ESI,m/z)精确质量计算C19H27O2Si[M+H+]:315.1775,实测值:315.1779。
实施例30
按照方法H制备,产物为无色油状物(Rf=0.5,石油醚),收率为70%(42mg),97%ee。用Daicel Chiralpak OD-3色谱柱分析(正己烷,1.0mL/min),λ=220nm,温度=28℃,tr(minor)=10.4min,tr(major)=10.9min。表征数据:[α]D 21.0=-49.4(c=1.0,CHCl3)。1HNMR(400MHz,CDCl3)δ7.50-7.47(m,2H),7.42-7.32(m,3H),7.13-7.08(m,4H),4.65(s,1H),3.84(t,J=7.2Hz,2H),2.89(t,J=7.2Hz,2H),2.25(s,3H),0.94(s,9H)。13C NMR(101MHz,CDCl3)δ136.96,136.54,134.66,133.86,130.21,130.05,129.97,127.85,126.44,125.95,65.31,36.34,25.76,19.49,18.09。HRMS(ESI,m/z)精确质量计算C19H27OSi[M+H+]:299.1826,实测值:299.1825。
实施例31
按照方法H制备,产物为无色油状物(Rf=0.2,石油醚),收率为83%(50mg),97%ee。用Daicel Chiralpak OD-3色谱柱分析(正己烷,0.6mL/min),λ=220nm,温度=28℃,tr(major)=9.5min,tr(minor)=9.9min。表征数据:[α]D 23.4=-46.2(c=1.0,CHCl3)。1H NMR(600MHz,CDCl3)δ7.48-7.46(m,2H),7.42-7.39(m,1H),7.36-7.33(m,2H),7.23-7.19(m,1H),6.96(d,J=7.8Hz,1H),6.91-6.87(m,2H),4.61(s,1H),3.87(t,J=7.2Hz,2H),2.85(t,J=7.2Hz,2H),0.92(s,9H)。13C NMR(151MHz,CDCl3)δ162.93(d,JCF=245.4Hz),141.76(d,JCF=7.3Hz),134.62,133.72,130.12,129.69(d,JCF=7.9Hz),127.89,124.98(d,JCF=2.2Hz),116.19(d,JCF=20.9Hz),113.13(d,JCF=21.4Hz),65.83,38.84,25.72,18.10。19FNMR(565MHz,CDCl3)δ-114.16。HRMS(ESI,m/z)精确质量计算C18H24FOSi[M+H+]:303.1575,实测值:303.1573。
实施例32
按照方法H制备,产物为无色油状物(Rf=0.5,石油醚),收率为66%(44mg),96%ee。用Daicel Chiralpak OD-3色谱柱分析(正己烷,0.6mL/min),λ=220nm,温度=28℃,tr(major)=5.2min,tr(minor)=6.8min。表征数据:[α]D 22.8=-43.3(c=1.0,CHCl3)。1H NMR(400MHz,CDCl3)δ7.50(d,J=8.4Hz,2H),6.93(d,J=8.4Hz,2H),4.64(s,1H),3.82(s,3H),3.66-3.61(m,2H),1.69-1.54(m,7H),1.26-1.09(m,6H),0.94(s,9H),0.89-0.84(m,2H)。13CNMR(151MHz,CDCl3)δ161.21,136.18,125.22,113.64,65.69,55.13,37.55,33.56,33.54,29.87,26.86,26.55,25.83,18.20。HRMS(ESI,m/z)精确质量计算C20H35O2Si[M+H+]:335.2401,实测值:335.2401。
实施例33
按照方法H制备,产物为白色固体(Rf=0.3,石油醚/乙酸乙酯=20∶1),收率为80%(70mg),96%ee。用Daicel Chiralpak OD-3色谱柱分析(正己烷/异丙醇=99.0∶1.0,1.0mL/min),λ=220nm,温度=28℃,tr(major)=5.1min,tr(minor)=5.5min。表征数据:[α]D 22.8=-40.7(c=1.0,CHCl3)。1H NMR(400MHz,CDCl3)δ7.50-7.47(m,2H),7.09-7.03(m,4H),6.90-6.84(m,4H),6.80(d,J=8.0Hz,2H),4.67(s,1H),4.08-3.96(m,4H),3.80(s,3H),0.95(s,9H)。13CNMR(101MHz,CDCl3)δ161.39,145.04,136.24,127.45,127.36,124.64,124.34,122.61,115.35,113.79,61.97,55.13,49.51,25.74,18.16。HRMS(ESI,m/z)精确质量计算C25H30NO2SSi[M+H+]:436.1761,实测值:436.1763。
从二氯甲烷-石油醚溶液中得到该化合物的X射线衍射的单晶,X射线晶体结构数据存放在Cambridge Crystallographic Data Center(编号CCDC 2053379),衍射数据用Mo-Kα辐射BrukerD8VENTURE收集,晶体结构如1所示,详细信息如下表所示。
实施例34
按照方法H制备,产物为白色固体(Rf=0.3,石油醚/乙酸乙酯=100∶1),收率为69%(55mg),97%de。用Daicel ChiralpakAD-3色谱柱分析(正己烷/异丙醇=99.0∶1.0,1.0mL/min),λ=220nm,温度=28℃,tr(minor)=5.0min,tr(major)=5.3min。表征数据:[α]D 22.4=-75.1(c=1.0,CHCl3)。1H NMR(400MHz,CDCl3)δ7.50(d,J=8.4Hz,2H),6.94(d,J=8.4Hz,2H),4.93(s,1H),4.67(d,J=6.8Hz,2H),4.53(d,J=6.0Hz,1H),4.29(dd,J=8.0,6.4Hz,1H),3.83(s,3H),3.70-3.60(m,2H),3.26(s,3H),1.48(s,3H),1.31(s,3H),0.95(s,9H)。13C NMR(151MHz,CDCl3)δ161.38,136.16,124.38,113.76,112.34,109.47,86.96,85.31,82.01,65.88,55.14,54.91,26.60,25.71,25.12,18.24。HRMS(ESI,m/z)精确质量计算C20H33O6Si[M+H+]:397.2041,实测值:397.2045。
实施例35
按照方法H制备,产物为白色固体(Rf=0.4,石油醚/乙酸乙酯=100∶1),收率为70%(67mg),94%de。用Daicel Chiralpak OD-3色谱柱分析(正己烷/异丙醇=99.5∶0.5,1.0mL/min),λ=220nm,温度=28℃,tr(minor)=8.6min,tr(major)=9.0min。表征数据:[α]D 23.0=-26.0(c=1.0,CHCl3)。1H NMR(400MHz,CDCl3)δ7.50(d,J=8.4Hz,2H),7.19(d,J=8.8Hz,1H),6.93(d,J=8.4Hz,2H),6.70(dd,J=8.0,2.8Hz,1H),6.61(d,J=2.8Hz,1H),4.70(s,1H),3.82(s,3H),3.76(s,3H),3.68(t,J=8.3Hz,1H),2.85-2.81(m,2H),2.29-2.24(m,1H),2.15-2.09(m,1H),2.04-1.96(m,1H),1.89-1.81(m,2H),1.61-1.19(m,7H),1.12-1.02(m,1H),0.94(s,9H),0.82(s,3H)。13C NMR(101MHz,CDCl3)δ161.18,157.53,138.14,136.19,132.96,126.48,125.74,113.91,113.53,111.57,83.78,55.31,55.10,49.76,44.17,44.13,38.98,37.29,30.58,29.98,27.37,26.53,25.80,23.32,18.26,11.63。HRMS(ESI,m/z)精确质量计算C30H43O3Si[M+H+]:479.2976,实测值:479.2980。
实施例36
按照方法H制备,产物为白色固体(Rf=0.3,石油醚/乙酸乙酯=100∶1),收率为99%(96mg),99%ee。用Daicel Chiralpak OD-3色谱柱分析(正己烷,1.0mL/min),λ=220nm,温度=28℃,tr(major)=24.8min,tr(minor)=31.3min。表征数据:[α]D 22.8=-12.5(c=1.0,CHCl3)。1H NMR(600MHz,CDCl3)δ7.96(d,J=8.4Hz,1H),7.61-7.58(m,1H),7.34-7.31(m,2H),7.29-7.28(m,2H),7.23-7.20(m,1H),7.19-7.16(m,1H),7.13-7.09(m,2H),6.86-6.84(m,J=8.5Hz,2H),4.73(q,J=11.4Hz,2H),4.57(s,1H),3.81(s,3H),2.61-2.56(m,1H),1.35-1.32(m,2H),1.05-1.02(m,2H),0.90(s,9H)。13C NMR(151MHz,CDCl3)δ163.09,162.60(d,JCF=252.0Hz),161.34,147.42,146.21,137.27,136.12,132.48(d,JCF=3.3Hz),131.74(d,JCF=15.2Hz),131.74,129.25,129.04(d,JCF=10.8Hz),126.54,126.26,125.39,124.31,115.29(d,JCF=7.7Hz),115.15(d,JCF=7.9Hz),113.64,61.79,55.14,25.68,18.15,14.81,10.04,10.00。19F NMR(565MHz,CDCl3)δ-114.24。HRMS(ESI,m/z)精确质量计算C30H33FNO2Si[M+H+]:486.2559,实测值:486.2564。
实施例37
按照方法H制备,产物为白色固体(Rf=0.4,石油醚/乙酸乙酯=100∶1),收率为52%(48mg),>99%ee,98∶2dr。用Daicel Chiralpak OD-3色谱柱分析(正己烷,1.0mL/min),λ=220nm,温度=28℃,tr(minor)=12.0min,tr(meso)=12.6min,tr(major)=13.1min。表征数据:[α]D 19.3=-33.7(c=1.0,CHCl3)。1H NMR(400MHz,CDCl3)δ7.60-7.58(m,4H),7.45-7.35(m,6H),7.28(s,4H),4.81-4.73(m,6H),0.99(s,18H)。13C NMR(101MHz,CDCl3)δ139.57,134.72,133.66,130.18,127.94,126.42,66.79,25.82,18.25。
实施例38
按照方法H制备,产物6a为白色固体(Rf=0.4,石油醚/乙酸乙酯=20∶1),收率为71%(56mg),93%ee。用Daicel Chiralpak AD-H色谱柱分析(正己烷/异丙醇=99.0∶1.0,1.0mL/min),λ=220nm,温度=28℃,tr(minor)=4.6min,tr(major)=4.8min。表征数据:[α]D 19.4=-63.6(c=1.0,CHCl3)。1H NMR(600MHz,CDCl3)δ8.58(d,J=9.0Hz,1H),8.25(d,J=7.8Hz,1H),8.18-8.16(m,3H),8.09-8.04(m,3H),7.98(t,J=7.8Hz,1H),7.36-7.30(m,4H),7.24(t,J=7.2Hz,1H),5.35(s,1H),4.88(q,J=13.2Hz,2H),1.08(s,9H)。13C NMR(151MHz,CDCl3)δ140.58,136.81,133.53,132.86,131.39,130.89,129.08,128.52,128.41,128.01,127.75,127.61,127.29,126.57,126.05,125.46,125.42,124.80,124.70,124.17,67.06,26.51,19.39。HRMS(APCI,m/z)精确质量计算C27H27OSi[M+H+]:395.1826,实测值:395.1837。
实施例39
按照方法H制备,产物6b为白色固体(Rf=0.4,石油醚/乙酸乙酯=20∶1),收率为93%(132mg),>93%ee,97∶3dr。用Daicel Chiralpak OD-3色谱柱分析(正己烷/异丙醇=99.0∶1.0,1.0mL/min),λ=220nm,温度=28℃,tr(major)=7.0min,tr(meso)=7.5min,tr(minor)=7.9min。表征数据:[α]D 20.1=-55.1(c=1.0,CHCl3)。1H NMR(600MHz,CDCl3)δ8.58(d,J=9.6Hz,2H),8.25(d,J=7.8Hz,2H),8.19-8.18(m,6H),8.12-8.06(m,6H),8.00(t,J=7.6Hz,2H),7.31(s,4H),5.34(s,2H),4.86(q,J=12.6Hz,4H),1.07(s,18H)。13C NMR(151MHz,CDCl3)δ139.49,136.80,133.55,132.85,131.40,130.90,129.13,128.52,128.03,127.73,127.62,126.61,126.06,125.47,125.42,124.81,124.69,124.17,66.95,26.52,19.38。HRMS(APCI,m/z)精确质量计算C48H46O25i2[M+]:710.3031,实测值:710.3044。
实施例40
参照方法H制备,区别在于:[Rh(cod)Cl]2(2.0mg,4mol%),L4(4.8mg,8.8mol%),1,4-二氧六环(2mL),二氢硅烷底物(0.12mmol,1.2当量),醇底物(0.1mmol,1.0当量)。产物6c为白色固体(Rf=0.4,石油醚/乙酸乙酯=20∶1),收率为40%(33mg),>99%ee,95:5dr。用Daicel Chiralpak AD-3色谱柱分析(正己烷/异丙醇=99.0∶1.0,1.0mL/min),λ=220nm,温度=28℃,tr(minor)=7.5min,tr(major)=7.9min,tr(meso)=8.3min。表征数据:[α]D 20.4=-39.9(c=1.0,CHCl3)。1H NMR(400MHz,CDCl3)δ8.55(d,J=9.2Hz,2H),8.26(d,J=7.6Hz,2H),8.17-8.03(m,12H),7.99-7.95(m,8H),7.89(d,J=9.2Hz,2H),5.56(s,4H),5.38(s,2H),1.09(s,18H)。13C NMR(101MHz,CDCl3)δ136.74,133.57,133.50,132.83,131.34,130.82,130.64,129.19,128.70,128.50,128.01,127.61,127.57,127.54,125.99,125.77,125.4l,125.34,124.90,124.74,124.71,124.63,124.13,122.95,65.99,26.56,19.37。HRMS(APCI,m/z)精确质量计算C58H50O2Si2[M+]:834.3343,实测值:834.3364。
实施例41
显示圆偏振发光(CPL)的手性分子在3D显示、自旋信息传递、信息存储和处理、CPL激光和生物探针等领域具有巨大的应用价值。本发明的化合物中,具有硅立体异构中心的发色团由于σ*-π*共轭具有潜在的CPL发射特性。
为了说明本发明的手性有机硅化合物的应用价值,检测了化合物6a-6c的光物理性质,在365nm的紫外光照射下,6a和6b在CH2Cl2中的溶液显示出蓝色发光,而6c显示出亮绿色的发光(图2a)。这些化合物显示出相似的紫外可见光谱,最大吸收分别在317nm、332nm和349nm处(图2b);化合物6a和6b的最大发射峰在396nm左右,这两个化合物在500nm左右都有一个比较小的宽峰,这可能是因为6a和6b形成了准分子。然而,化合物6c只出现准分子发射峰,这可能归因于化合物6c分子内有多个距离比较近的芘单元,从而产生堆积效应(图2c)。此外,与6a和6b相比,6c具有更大的斯托克斯位移(159nm)和更高的绝对荧光量子产率(0.55),是一类具有潜在应用价值的手性荧光材料。进一步通过圆二色谱(CD)和圆偏振发射光谱(CPL)研究了这些π共轭硅手性硅醚化合物。其中6a,6b及其对映异构体在约330nm和348nm处显示出清晰的Cotton效应,CD光谱互为镜像,而(R,R)-6c和(S,S)-6c在约330nm和355nm处表现出较强的相反信号(图2d)。CPL实验可以反映化合物发射激发态的手性,6a-6c均具有CPL活性,每对对映异构体都有清晰镜像(图2e),(R,R)-6c和(S,S)-6c有两个硅立体异构中心和三个芘基,从470nm到675nm具有强CPL信号。在573nm,(R,R)-6c的发光不对称因子(glum)为-1.1×10-2,(S,S)-6c的发光不对称因子为+1.1×10-2(图2f)。手性有机小分子化合物具有如此高的g1um值和以及荧光量子效率(化合物6a,glum:0.0075,ΦF:0.34;化合物6b,g1um:0.0077,ΦF:0.43;化合物6c,glum:0.011,ΦF:0.55)是非常罕见的。因此,利用本发明方法获得的这些化合物,其显著的CPL特性,会在CPL光学显示、信息存储、生物探针、CPL激光等领域具有广泛的应用前景。
以上所述,仅为本发明的具体实施方式,但本发明的保护范围并不局限于此,任何属于本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应该以权利要求的保护范围为准。
Claims (4)
4.根据权利要求3所述的制备方法,其特征在于,所述铑催化剂为[Rh(cod)Cl]2;所述配体的用量至少是2mol%,所述铑催化剂的用量至少是1mol%;所述式II化合物和(R3)3SiOH或R4OH的摩尔比为(1~3):1;所述反应的温度为0℃以上。
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