本方法涉及一種手性二氫硅烷化合物及其合成方法和應(yīng)用,尤其是涉及一種光學(xué)活性的硅烷化合物的合成方法。
背景技術(shù):
:手性廣泛存在于自然界中,“沙利度胺事件”使人們逐漸認(rèn)識(shí)到了手性的重要性。不對(duì)稱催化反應(yīng)是制備手性化合物的重要途徑。在不對(duì)稱催化反應(yīng)中,金屬催化是非常重要的一個(gè)手段,但不同金屬在地球上的含量是不一樣的,且有些金屬具有一定的毒性,因此,利用地球豐產(chǎn)的廉價(jià)的低毒或者無毒的金屬進(jìn)行不對(duì)稱催化具有重要意義,尤其在藥物和材料領(lǐng)域有廣闊的應(yīng)用前景。硅氫化反應(yīng)目前被廣泛用于制備含有碳-碳雙鍵、碳-碳叁鍵、碳-氧雙鍵、碳-氮雙鍵、碳-氮叁鍵、氮-氮雙鍵和氮-氧鍵的一系列有機(jī)硅化合物[a)k.tamao,n.ishida,t.tanaka,m.kumada,organometallics1983,2,1694;b)i.fleming,r.henning,h.plaut,j.chem.soc.chem.commun.1984,29.]。硅氫化反應(yīng)還在合成天然有機(jī)化合物中作保護(hù)基和還原劑等[a)y.hatanaka,t.hiyama,j.org.chem.1988,53,918;b)s.e.denmark,c.s.regens,acc.chem.res.2008,41,1486.]。硅材料是重要的半導(dǎo)體材料,有機(jī)硅化合物在生物醫(yī)藥領(lǐng)域也有重要的應(yīng)用。烯烴的硅氫化反應(yīng)是制備有機(jī)硅材料的重要途徑。在烯烴的硅氫化反應(yīng)中,硅氫鍵扮演著非常重要的角色。由于硅氫鍵具有較高的反應(yīng)活性,因此,通過對(duì)硅氫鍵的延伸化,可以獲得更多更豐富的含硅化合物?;衔镏泻休^多的硅氫鍵,能為后續(xù)延伸化提供更多的空間。因此,含有兩個(gè)硅氫鍵的硅烷,由于其既具有一定的取代基基礎(chǔ),又具有一定的硅氫鍵,常常被用來作為合成有機(jī)硅化合物的中間體。(nielsen,l.;skrydstrup,t.j.am.chem.soc.2008,130,13145–13151)1976年,kumada發(fā)展了烯烴的不對(duì)稱硅氫化反應(yīng)[yamamoto,k.;hayashi,t.;zembayashi,m.;kumada,m.j.organomet.chem.1976,118,161],但是對(duì)映體選擇性較低(0.6-20.9%ee)。1991年,hayashi發(fā)展了鈀催化的氯硅烷作為硅試劑的簡單烯烴的不對(duì)稱硅氫化反應(yīng)[uozumi,y.;hayashi,t.j.am.chem.soc.1991,113,9887],后來又有研究小組發(fā)展了一系列的手性膦配體應(yīng)用于烯烴的不對(duì)稱硅氫化反應(yīng),但是所用硅試劑都含有氯或者氟,這大大限制了其官能團(tuán)容忍性[鈀催化的烯烴的不對(duì)稱硅氫化反應(yīng)綜述:a)gibson,s.e.;rudd,m.adv.synth.catal.2007,349,781;鈀催化的烯烴的不對(duì)稱硅氫化反應(yīng)實(shí)例:b)uozumi,y.;hayashi,t.j.am.chem.soc.1991,113,9887;c)kitayama,k.;uozumi,y.;hayashi,t.j.chem.soc.,chem.commun.1995,1533;d)weber,i.;jones,g.b.tetrahedronlett.2001,42,6983;e)shimada,t.;mukaide,k.;shinohara,a.;han,j.w.;hayashi,t.j.am.chem.soc.2002,124,1584;f)jensen,j.f.;svendsen,b.y.;lacour,t.v.;pedersen,h.l.;johannsen,m.j.am.chem.soc.2002,124,4558;g)guo,x.;xie,j.;hou,g.;shi,w.;wang,l.;zhou,q.tetrahedron:asymmetry.2004,15,2231;h)rendler,s.;r.;keller,m.;oestreich,m.eur.j.org.chem.2008,2582;i)zhang,f.;fan,q.org.biomol.chem.2009,7,4470;j)junge,k.;wendt,b.;enthaler,s.;beller,m.chemcatchem2010,2,453;銠催化的烯烴的不對(duì)稱硅氫化反應(yīng)綜述:k)ito,j.-i.;nishiyama,h.organomet.chem.2011,37,185;稀有過渡金屬催化的烯烴不對(duì)稱硅氫化反應(yīng)實(shí)例:l)fu,p.-f.;brard,l.;li,y.;marks,t.j.j.am.chem.soc.1995,117,7157;m)gountchev,t.i.;tilley,t.d.organometallics1999,18,5661.].tamao和bosnich分別獨(dú)立地發(fā)展了以硅烷作為硅試劑的分子內(nèi)烯烴不對(duì)稱硅氫化反應(yīng)[a)tamao,k.;tohma,t.;inui,n.;nakayama,o.;ito,y.tetrahedronlett.1990,31,7333.b)bergens,s.h.;noheda,p.;whelan,j.;bosnich,b.j.am.chem.soc.1992,114,2121.]。除此之外,對(duì)于利用不含鹵素的硅烷作為硅試劑的分子間烯烴不對(duì)稱硅氫化反應(yīng),只有以環(huán)乙烯基酯或降冰片烯為底物的幾個(gè)例子(a)m.b.haque,b.p.roberts,d.a.tocher,j.chem.soc.,perkintrans.i1998,2881;b)t.i.gountchev,t.d.tilley,organometallics1999,18,5661.),或者是1,1-二取代烯烴的馬氏加成硅氫化反應(yīng),但其只有中等的ee值(p.-f.fu,l.brard,y.li,t.j.marks,j.am.chem.soc.1995,117,7157)。2012年,nishiyamaandco-workers報(bào)道了銠催化的以三取代硅烷作為硅試劑的烯烴不對(duì)稱硅氫化反應(yīng),但大多情況下其只有中等的區(qū)域選擇性(30/70~91/9b/l)(t.naito,t.yoneda,j.-i.ito,h.nishiyama,synlett,2012,23,2957.)。2017年,lugroup報(bào)道了炔烴的不對(duì)稱硅氫化/氫化串聯(lián)反應(yīng)來合成手性硅化合物,但其對(duì)于脂肪族的底物是不適用的,而且只能合成三取代的手性硅化合物。(guo,j.;shen,x.;lu,z.angew.chem.int.ed.2017,56,615.)隨后,buchwaldgroup報(bào)道了手性雙膦配體、銅催化的烯烴不對(duì)稱硅氫化反應(yīng),但其需要用到過量的硅烷(1.5~5equiv)反應(yīng)12-72小時(shí),且其手性二取代的硅氫化產(chǎn)物只能作為中間體通過tamao氧化轉(zhuǎn)化為手性醇化合物,此外,對(duì)于脂肪族的底物也是不適用的。(gribblejr.,m.w.;pirnot,m.t.;bandar,j.s.;liu,r.y.;buchwald,s.l.j.am.chem.soc.2017,139,2192.)因此,發(fā)展高效率高選擇性的地球豐產(chǎn)金屬催化的烯烴的不對(duì)稱硅氫化反應(yīng)合成手性二氫硅烷化合物有著重大的意義。技術(shù)實(shí)現(xiàn)要素:本發(fā)明要解決的問題是提供一種有效合成手性二氫硅烷化合物的方法,是由手性cox2-oip絡(luò)合物催化烯烴和硅烷的硅氫化反應(yīng),高效率高對(duì)映體選擇性地合成光學(xué)活性的二氫硅烷化合物的方法。本發(fā)明是通過以下技術(shù)方案來實(shí)現(xiàn)的:一種手性二氫硅烷化合物,所述手性二氫硅烷化合物如式iv所示:式iv中,*代表手性碳原子;r1,r2任選自c1-c16的烷基、c3-c16的環(huán)烷基、芐基、萘基、鄰苯二甲酰亞胺基、式v所示的基團(tuán)或c4~c10的含n、o、s的雜環(huán)芳基a;所述烷基、環(huán)烷基上的h不被取代或被1個(gè)以上的取代基a取代,所述取代基a包括硝基、鹵素、苯基、鄰苯二甲酰亞胺基、雜環(huán)芳基b、甲氧羰基、羰基、三氟甲基、羥基、c1~c3的醛基、c1~c3的羧基、氨基、c1~c3的酯基或酰胺基;所述雜環(huán)芳基b包括吲哚基、噻吩基、吡啶基或喹啉基;所述芐基、萘基、含n、o、s的雜環(huán)芳基a上的h不被取代或被1個(gè)以上的取代基b取代,所述取代基b包括c1~c3的烷基、c1~c3的烷氧基、硝基、鹵素、苯基、甲氧羰基、三氟甲基、羥基、羰基、c1~c3的醛基、c1~c3的羧基、氨基、c1~c3的酯基、酰胺基或鄰苯二甲酰亞胺基;所述含n、o、s的雜環(huán)芳基a包括噻吩基、苯并噻吩基、吲哚基、n-甲基吲哚基、吡啶基、喹啉基或呋喃基;式v中,r3、r4、r5、r6、r7任選自h、鹵素、c1-c16的烷基、c1-c16的烷氧基、c1-c16的烷硫基、苯基、三氟甲基、甲氧羰基、硝基、羥基、c1~c3的醛基、c1~c3的羧基、氨基、c1~c3的酯基、酰胺基、乙酰氧甲基、2-甲基-1,3-二氧環(huán)戊基中的任意一種。進(jìn)一步,優(yōu)選所述r1為c1-c10的烷基、萘基、n-甲基吲哚基、噻吩基、苯并噻吩基、吡啶基、2-甲氧基吡啶基或式v所示的基團(tuán);所述烷基的h不被取代或被1個(gè)以上的取代基a取代,所述取代基a為硝基、鹵素、苯基、羥基、羰基、c1~c3的醛基、c1~c3的羧基、氨基、鄰苯二甲酰亞胺基、吲哚基、噻吩基或吡啶基;優(yōu)選r2為式v所示的基團(tuán);式v所示的基團(tuán)優(yōu)選為苯基或含有1~2個(gè)以下取代基的取代苯基:甲基、丁基、苯基、甲氧基、甲硫基、f、cl、br、三氟甲基、甲氧羰基、乙酰氧甲基、2-甲基-1,3-二氧環(huán)戊基。更進(jìn)一步,優(yōu)選所述r1為苯基、對(duì)甲基苯基、對(duì)丁基苯基、聯(lián)苯基、對(duì)甲氧基苯基、對(duì)甲硫基苯基、對(duì)氟苯基、對(duì)氯苯基、對(duì)溴苯基、對(duì)三氟甲基苯基、對(duì)甲氧羰基苯基、對(duì)乙酰氧甲基苯基、4-(2-甲基-1,3-二氧環(huán)戊基)苯基、間三氟甲基苯基、間氯苯基、間甲基苯基、鄰甲基苯基、3-甲氧基-4-氟苯基、1-萘基、2-萘基、n-甲基吲哚基、噻吩基、苯并噻吩基、2-甲氧基吡啶基、ch3(co)ch2ch2-、正己基、溴代丙基、1-羥基-丁基或異吲哚-1,3-二酮取代的壬基。優(yōu)選r2為苯基、對(duì)甲氧基苯基或?qū)β缺交?。本發(fā)明還提供所述手性二氫硅烷化合物的合成方法,所述方法為:以式i所示的烯烴和式ii所示的硅烷為原料,手性cox2-oip絡(luò)合物為催化劑,在還原劑存在下,反應(yīng)制得式iv所示的手性二氫硅烷化合物;r2sih3ii式i或式ii中,r1,r2任選自c1-c16的烷基(優(yōu)選c1-c10的烷基,更優(yōu)選c1-c6的烷基)、c3-c16的環(huán)烷基(優(yōu)選c3-c10的環(huán)烷基,更優(yōu)選c3-c6的環(huán)烷基),芐基、萘基、鄰苯二甲酰亞胺基、式v所示的基團(tuán)或c4~c10的含n、o、s的雜環(huán)芳基a;所述含n、o、s的雜環(huán)芳基a包括噻吩基、苯并噻吩基、吲哚基、n-甲基吲哚基、吡啶基、喹啉基、呋喃基等;所述烷基、環(huán)烷基上的h不被取代或被1個(gè)以上的取代基a取代,所述取代基a包括硝基、鹵素、苯基、鄰苯二甲酰亞胺基、雜環(huán)芳基b、甲氧羰基、羰基、三氟甲基、羥基、c1~c3的醛基、c1~c3的羧基、氨基、c1~c3的酯基或酰胺基;所述雜環(huán)芳基b包括吲哚基、噻吩基、吡啶基、喹啉基等;所述芐基、萘基、含n、o、s的雜環(huán)芳基a上的h不被取代或被1個(gè)以上的取代基b取代,所述取代基b包括c1~c3的烷基、c1~c3的烷氧基、硝基、鹵素、苯基、甲氧羰基、三氟甲基、羥基、羰基、c1~c3的醛基、c1~c3的羧基、氨基、c1~c3的酯基、酰胺基或鄰苯二甲酰亞胺基;式v中,r3、r4、r5、r6、r7任選自h、鹵素、c1-c16的烷基(優(yōu)選c1-c10的烷基,更優(yōu)選c1-c6的烷基)、c1-c16的烷氧基(優(yōu)選c1-c10的烷氧基,更優(yōu)選c1-c6的烷氧基)、c1-c16的烷硫基(優(yōu)選c1-c10的烷硫基,更優(yōu)選c1-c6的烷硫基)、苯基、三氟甲基、甲氧羰基、硝基、羥基、c1~c3的醛基、c1~c3的羧基、氨基、c1~c3的酯基、酰胺基、乙酰氧甲基、2-甲基-1,3-二氧環(huán)戊基中的任意一種。鹵素包括f、cl、br或i;r3,r4,r5,r6,r7全為h時(shí),式v所示的基團(tuán)即為苯基;優(yōu)選式v所示的基團(tuán)為苯基或含有1~2個(gè)以下取代基的取代苯基:甲基、丁基、苯基、甲氧基、甲硫基、f、cl、br、三氟甲基、甲氧羰基、乙酰氧甲基、2-甲基-1,3-二氧環(huán)戊基進(jìn)一步,優(yōu)選r1為c1-c10的烷基、萘基、n-甲基吲哚基、噻吩基、苯并噻吩基、吡啶基、2-甲氧基吡啶基式v所示的基團(tuán);所述烷基的h不被取代或被1個(gè)以上的取代基a取代,所述取代基a優(yōu)選硝基、鹵素、苯基、羥基、羰基、c1~c3的醛基、c1~c3的羧基、氨基、鄰苯二甲酰亞胺基、吲哚基、噻吩基、吡啶基等;優(yōu)選r2為式v所示的基團(tuán)。進(jìn)一步,優(yōu)選r1為苯基、對(duì)甲基苯基、對(duì)丁基苯基、聯(lián)苯基、對(duì)甲氧基苯基、對(duì)甲硫基苯基、對(duì)氟苯基、對(duì)氯苯基、對(duì)溴苯基、對(duì)三氟甲基苯基、對(duì)甲氧羰基苯基、對(duì)乙酰氧甲基苯基、4-(2-甲基-1,3-二氧環(huán)戊基)苯基、間三氟甲基苯基、間氯苯基、間甲基苯基、鄰甲基苯基、3-甲氧基-4-氟苯基、1-萘基、2-萘基、n-甲基吲哚基、噻吩基、苯并噻吩基、2-甲氧基吡啶基、ch3(co)ch2ch2-、、1-羥基-丁基、正己基、溴代丙基或異吲哚-1,3-二酮取代的壬基。優(yōu)選r2為苯基、對(duì)甲氧基苯基或?qū)β缺交景l(fā)明所用的催化劑為手性cox2-oip絡(luò)合物(oip:亞胺吡啶噁唑啉配體),結(jié)構(gòu)式為式iii所示的化合物或其對(duì)映體,所述對(duì)映體即為式iii的鏡像。r8,r9,r10,r11,r12,r13,r14,r15,r16,r17,r18,r19任選自h、c1-c16的烷基、c1-c16的烷氧基、鹵素、苯基、萘基或芐基:所述烷基、烷氧基上的h不被取代或被1個(gè)以上的取代基c取代,所述取代基c包括硝基、鹵素、苯基、甲氧羰基、羰基、三氟甲基、羥基、c1~c3的醛基、c1~c3的羧基、氨基、c1~c3的酯基或酰胺基;所述苯基、芐基、萘基上的h不被取代或被1個(gè)以上的取代基d取代,所述取代基d包括c1~c3的烷基、c1~c3的烷氧基、硝基、鹵素、苯基、甲氧羰基、羰基、三氟甲基、羥基、c1~c3的醛基、c1~c3的羧基、氨基、c1~c3的酯基或酰胺基;x為f、cl、br、i、oac、cf3so3中的任意一種。進(jìn)一步,式iii中,優(yōu)選r8為c1-c4的烷基或芐基、r9為c1-c4的烷基或二苯基次甲基(-chph2),r10為h,r11為c1-c4的烷基、c1-c4的烷氧基或鹵素;r12為h;r13為c1-c4的烷基或二苯基次甲基(-chph2);r14為甲基;r15、r16、r17、r18、r19均為h,x優(yōu)選為cl。更優(yōu)選的,所用的催化劑如式iii-1所示bn代表芐基,ph代表苯基,meo代表甲氧基;本發(fā)明合成方法的反應(yīng)式如下所示作為進(jìn)一步地改進(jìn),本發(fā)明所述的所述合成方法可在無溶劑或在有機(jī)溶劑中進(jìn)行,在有機(jī)溶劑中反應(yīng)時(shí),所述的有機(jī)溶劑可以為苯、四氯化碳、甲苯、四氫呋喃、乙醚、二氯甲烷、乙腈、二氧六環(huán)、石油醚、環(huán)己烷、正己烷、乙酸乙酯、三氯甲烷、n,n-二甲酰胺中的任意一種,優(yōu)選乙醚。所述有機(jī)溶劑的體積用量一般以式i所示的烯烴的物質(zhì)的量計(jì)為1~10ml/mmol。作為進(jìn)一步地改進(jìn),本發(fā)明所述的所述合成方法中優(yōu)選在無溶劑條件下或乙醚溶劑中進(jìn)行。作為進(jìn)一步地改進(jìn),本發(fā)明所述的式ii所示的硅烷、式i所示的烯烴、手性cox2-oip絡(luò)合物、還原劑的物質(zhì)的量之比為1:0.1-10:0.0000005-0.05:0.0000005-0.15,優(yōu)選為1:0.1-10:0.0005-0.05:0.0015-0.15,更優(yōu)選為1:0.5-2:0.001-0.05:0.001-0.15;最優(yōu)選為1:1~1.2:0.01~0.05:0.03~0.15。作為進(jìn)一步地改進(jìn),本發(fā)明所述的所述合成方法中,反應(yīng)溫度為-30℃~80℃,優(yōu)選-10℃~60℃,尤其推薦0~25℃。本發(fā)明反應(yīng)的反應(yīng)時(shí)間優(yōu)選3分鐘-48小時(shí),優(yōu)選為30分鐘-12小時(shí),尤其推薦1小時(shí)本發(fā)明的還原劑為三乙基硼氫化鈉、三仲丁基硼氫化鈉、三乙基硼氫化鋰、叔丁醇鈉、叔丁醇鉀、叔丁醇鋰、叔戊醇鈉、乙醇鈉、甲醇鈉、甲醇鉀中的任意一種,優(yōu)選三乙基硼氫化鈉、叔丁醇鈉、乙醇鈉或甲醇鈉,更優(yōu)選為叔丁醇鈉。作為進(jìn)一步地改進(jìn),本發(fā)明反應(yīng)結(jié)束后,所得粗產(chǎn)物經(jīng)過后處理制得式iv所示的手性二氫硅烷化合物,進(jìn)一步,所述后處理方法為下列一種或兩種以上:重結(jié)晶、薄層層析、柱層析或減壓蒸餾,優(yōu)選為柱層析。本發(fā)明方法提供了一種有效的由手性cox2-oip絡(luò)合物為催化劑,由烯烴和硅烷高效率高對(duì)映體選擇性的合成光學(xué)活性的硅烷化合物的方法。與現(xiàn)有方法相比,該方法適用于多種不同類型的烯烴,反應(yīng)條件溫和,操作簡便,原子經(jīng)濟(jì)性高。另外,反應(yīng)無需其他任何的有毒過渡金屬(如釕、銠、鈀等)鹽類的加入,在藥物和材料合成上具有較大的實(shí)際應(yīng)用價(jià)值。且反應(yīng)的產(chǎn)率也較好,一般為53%~97%,對(duì)映體選擇性也較高,一般為81%~>99%。本發(fā)明方法制得的式iv所示的手性二氫硅烷化合物可用于氧化合成手性醇類化合物,手性硅醇類化合物,手性多取代硅烷類化合物等。常規(guī)外消的二氫硅烷化合物用于合成醇類化合物、硅醇類化合物、多取代硅烷類化合物都屬于公知的方法,本發(fā)明合成出來的手性二氫硅烷同樣適用,只是以手性二氫硅烷為原料代替外消原料,可以合成出相應(yīng)手性的產(chǎn)物,因此本申請(qǐng)的手性二氫硅烷可進(jìn)一步用于光學(xué)活性的有機(jī)硅化合物的合成,具有較大的應(yīng)用價(jià)值。進(jìn)一步,所述式iv所示的手性二氫硅烷化合物用于氧化合成手性醇類化合物,所述應(yīng)用的方法是將式iv所示的手性二氫硅烷經(jīng)tamao氧化,反應(yīng)得到如式a所示的手性醇類化合物。反應(yīng)式如下式所示:進(jìn)一步,所述tamao氧化的反應(yīng)條件一般為:式iv所示的手性二氫硅烷與四氟硼酸-乙醚絡(luò)合物催化劑攪拌反應(yīng)后,再與氟化鉀、碳酸氫鉀、雙氧水反應(yīng),制得式a所示的手性醇類化合物;進(jìn)一步,優(yōu)選所述tamao氧化的反應(yīng)步驟為:式iv所示的手性二氫硅烷與四氟硼酸-乙醚絡(luò)合物催化劑在二氯甲烷溶劑中,在0℃攪拌反應(yīng)3h,除去溶劑,加入四氫呋喃、甲醇、氟化鉀、碳酸氫鉀、雙氧水,室溫?cái)嚢璺磻?yīng)15h,加水稀釋,乙醚萃取、洗滌、干燥后,除去溶劑后經(jīng)柱層析分離制得式a所示的手性醇類化合物;所述式iv所示的手性二氫硅烷、四氟硼酸-乙醚絡(luò)合物、氟化鉀、碳酸氫鉀、h2o2的物質(zhì)的量之比為1:5~8:4~5:10:40~50進(jìn)一步,所述式iv所示的手性二氫硅烷化合物用于合成手性硅醇類化合物,所述應(yīng)用的方法包括以下兩種:(1)式iv所示的手性二氫硅烷化合物在三氯化硼催化劑的作用下,反應(yīng)得到式b所示的手性一羥基硅烷化合物;反應(yīng)溶劑通常為二氯甲烷和水(2)式iv所示的手性二氫硅烷化合物在鈀碳催化劑的作用下,反應(yīng)得到式c所示的手性二羥基硅烷化合物;反應(yīng)溶劑通常為乙醚和水反應(yīng)式如下所示:進(jìn)一步,所述式iv所示的手性二氫硅烷化合物用于手性多取代硅烷類化合物,所述應(yīng)用的方法包括以下兩種:(1)將式iv所示的手性二氫硅烷化合物與式d所示的烯基化合物反應(yīng),在金屬絡(luò)合物催化劑和還原劑作用下,反應(yīng)得到如式e或式f所示的手性多取代硅烷類化合物;(2)將式iv所示的手性二氫硅烷化合物與式g所示的炔基化合物反應(yīng),在金屬絡(luò)合物催化劑和還原劑作用下,反應(yīng)得到如式h或式j(luò)所示的手性多取代烯基硅烷類化合物;所述的金屬絡(luò)合物催化劑優(yōu)選iproip-fecl2、xantphos-cobr2或2,4-dmboip.cobr2等。所述的還原劑為三乙基硼氫化鈉、三仲丁基硼氫化鈉、三乙基硼氫化鋰、叔丁醇鈉、叔丁醇鉀、叔丁醇鋰、叔戊醇鈉、乙醇鈉、甲醇鈉、甲醇鉀中的任意一種,優(yōu)選三乙基硼氫化鈉反應(yīng)式如下式所示:本發(fā)明的方法是一種有效的由烯烴和硅烷合成手性二氫硅烷化合物的方法。該方法是用cox2-oip絡(luò)合物作為催化劑,尤其是以手性的cox2-oip絡(luò)合物作為催化劑時(shí)能夠由烯烴和硅烷高效率高對(duì)映體選擇性的合成光學(xué)活性的二氫硅烷化合物。附圖說明圖1催化劑手性cox2-oip絡(luò)合物iii-1的單晶結(jié)構(gòu)圖。具體實(shí)施方式下面通過具體實(shí)施例對(duì)本發(fā)明的技術(shù)方案作進(jìn)一步地具體說明,但本發(fā)明的保護(hù)范圍不限于此:實(shí)施例1:手性cox2-oip絡(luò)合物催化的烯烴和硅烷的硅氫化反應(yīng)室溫下,在一干燥的反應(yīng)試管中加入手性cox2-oip絡(luò)合物(0.01mmol),式i所示的烯烴(1.0mmol),式ii所示的硅烷(1.0mmol),乙醚(2ml),叔丁醇鈉(0.03mmol),然后在室溫或0℃下攪拌1小時(shí)后柱層析分離(洗脫溶劑為石油醚或石油醚和乙酸乙酯的混合物)得到產(chǎn)物。實(shí)施例1中,手性cox2-oip絡(luò)合物的化學(xué)式如下式iii-1所示:制備方法參考文獻(xiàn):(a)dai,s.;sui,x.;chen,c.angew.chem.int.ed.2015,54,9948-9953.(b)greenhalgh,m.d.;thomas,s.p.j.am.chem.soc.,2012,134,11900-11903.(c)leonard,w.r.;romine,j.l.;meyers,a.i.j.org.chem.1991,56,1961-1963.(d)xi,t.;mei,y.c.;lu,z.org.lett.2015,17,5939-5941.(e)guo,j.;shen,x.z.;lu,z.angew.chem.int.ed.2017,56,615-618.具體制備方法如下:將2,6-二二苯甲基-4-甲氧基苯胺(4.6g,10mmol)(參照文獻(xiàn)(a)做出),2-溴-6-乙?;拎?2.4g,12mmol),對(duì)甲苯磺酸一水合物(0.19g,1mmol),60ml甲苯放入100ml圓底燒瓶中,圓底燒瓶接分水器,在150℃加熱回流24h,冷卻至室溫,抽濾除去對(duì)甲苯磺酸。利用旋轉(zhuǎn)蒸發(fā)除去濾液中的溶劑,殘留物加入60ml乙醇,-25℃下攪拌,固體析出后抽濾,用10ml乙醇洗滌2次,得到黃色固體vi(4.92g,7.7mmol,77%產(chǎn)率)。熔點(diǎn):177-178℃;ir:3060,3026,2924,1643,1598,1552,1450,1305;1hnmr(cdcl3,400mhz):δ7.91(d,j=7.6hz,1h),7.58-7.47(m,2h),7.25-7.12(m,12h),7.01(dd,j=8.0,7.2hz,8h),6.44(s,2h),5.21(s,2h),3.55(s,3h),1.13(s,3h);13cnmr:(cdcl3,100mhz):δ169.1,157.1,155.2,143.2,142.1,141.7,140.7,138.4,133.4,129.7,129.4,129.0,128.3,128.0,126.4,126.1,120.0,113.7,55.1,52.2,16.8;hrms(ei)calculatedfor[c40h33n2obr]+,requiresm/z636.1776foundm/z636.1775.在氮?dú)獗Wo(hù)下,向干燥的schlenk管中加入vi(2.55g,4.0mmol),醋酸鈀(0.023g,0.10mmol),1,2-雙二苯基膦乙烷(0.051g,0.13mmol),叔丁醇鋰(0.66g,8.3mmol),1,4-二氧六環(huán)(25ml)和(s)-4-芐基-4,5-二氫噁唑啉(0.79g,4.9mmol)(參照文獻(xiàn)(c)做出)。schlenk管用液氮脫氣三次,反應(yīng)混合物在110℃油浴中攪拌42小時(shí),然后冷卻到室溫,倒入放有硅膠的砂芯抽濾,二氯甲烷淋洗(10ml×3)。旋轉(zhuǎn)蒸發(fā)移除溶劑后,用石油醚:乙酸乙酯(10:1)混合溶劑作為流動(dòng)相,硅膠作為固定相,進(jìn)行柱層析色譜分離得到黃色固體vii(1.79g,2.5mmol,62%產(chǎn)率)。熔點(diǎn):77-78℃;ir:2956,2924,1641,1459,1373;1hnmr(cdcl3,400mhz):δ8.08(dd,j=8.0,10.8hz,2h),7.76(dd,j=8.0,7.6hz,1h),7.35-7.23(m,5h),7.23-7.10(m,12h),7.00(d,j=6.8hz,8h),6.45(s,2h),5.25(s,2h),4.71-4.60(m,1h),4.45(dd,j=8.8,9.2hz,1h),4.25(t,j=8.0hz,1h),3.55(s,3h),3.30(dd,j=5.2,14hz,1h),2.78(dd,j=9.2,14hz,1h),1.45(s,3h);13cnmr:(cdcl3,100mhz):δ169.5,163.4,156.1,155.1,145.7,143.1,142.4,142.4,141.9,137.8,136.6,133.5,133.4,129.7,129.4,129.3,128.6,128.3,128.0,126.6,126.3,126.1,125.2,123.2,113.7,107.7,72.5,68.1,55.1,52.2,46.7,41.7,16.9;hrms(ei)calculatedfor[c50h43n3o2]+,requiresm/z717.3355foundm/z717.3356在n2保護(hù)下,向干燥的schlenk管中加入vii(1.51g,2.1mmol),thf(25ml),cocl2(0.25g,1.9mmol)。反應(yīng)混合物在25℃下攪拌13h后,注射25ml乙醚進(jìn)入反應(yīng)混合物,繼續(xù)攪拌2h。反應(yīng)混合物過濾,固體用乙醚(50ml)洗滌,在真空下干燥,得到棕色粉末(1.34g,1.6mmol,83%產(chǎn)率)。iii-1的單晶結(jié)構(gòu)如圖1所示,ccdc號(hào):1542890iv-1:(s)-1-苯基乙基苯硅烷(s)-phenyl(1-phenylethyl)silane油狀液體,87%產(chǎn)率,[α]20d=-18.1(c0.94,chcl3),99.3%ee,ir(cm-1):3023,2955,2924,2137,1600,1457.1hnmr(cdcl3,400mhz):δ7.44-7.35(m,3h),7.34-7.28(m,2h),7.28-7.21(m,2h),7.16-7.06(m,3h),4.35-4.29(m,2h),2.67-2.57(m,1h),1.45(d,j=7.6hz,3h);13cnmr:(cdcl3,100mhz):δ144.5,135.6,131.4,129.7,128.4,127.8,127.1,125.0,25.4,16.4.hrms(ei)calculatedfor[c14h16si]+requiresm/z212.1021,foundm/z212.1019.iv-2:(s)-1-對(duì)甲苯基乙基苯硅烷(s)-phenyl(1-(p-tolyl)ethyl)silane油狀液體,86%yield,[α]20d=-18.1(c1.11,chcl3),99.5%ee,ir(cm-1):3018,2954,2135,1511,1456,1014.1hnmr(cdcl3,400mhz):δ7.45-7.35(m,3h),7.34-7.28(m,2h),7.07(d,j=8.0hz,2h),7.00(d,j=8.0hz,2h),4.33-4.27(m,2h),2.62-2.53(m,1h),2.31(s,3h),1.43(d,j=7.4hz,3h);13cnmr:(cdcl3,100mhz):δ141.4,135.6,134.4,131.6,129.7,129.1,127.8,127.0,24.8,20.9,16.6.hrms(ei)calculatedfor[c15h18si]+requiresm/z226.1178,foundm/z226.1175.iv-3:(s)-1-((對(duì)叔丁基苯基)乙基)苯硅烷(s)-(1-(4-(tert-butyl)phenyl)ethyl)(phenyl)silane油狀液體,87%yield,[α]20d=-12.4(c0.98,chcl3),99.6%ee,ir(cm-1):2959,2135,1512,1459,1116.1hnmr(cdcl3,400mhz):δ7.44-7.35(m,3h),7.33-7.25(m,4h),7.04(d,j=8.4hz,2h),4.34-4.27(m,2h),2.64-2.54(m,1h),1.44(d,j=7.6hz,3h),1.31(s,9h);13cnmr:(cdcl3,100mhz):δ147.7,141.3,135.6,131.7,129.7,127.8,126.7,125.2,34.3,31.4,24.6,16.4.hrms(ei)calculatedfor[c18h24si]+requiresm/z268.1647,foundm/z268.1645.iv-4:(s)-1-(4-苯基苯基)乙基苯硅烷(s)-(1-([1,1'-biphenyl]-4-yl)ethyl)(phenyl)silane白色固體,88%yield,熔點(diǎn):89-91℃,opticalrotation:[α]20d=-18.7(c1.13,chcl3),99.7%ee,ir(cm-1):2955,2924,2132,1461,1378,1119.1hnmr(cdcl3,400mhz):δ7.61-7.55(m,2h),7.49(d,j=8.4hz,2h),7.46-7.36(m,5h),7.35-7.28(m,3h),7.16(d,j=7.8hz,2h),4.39-4.32(m,2h),2.71-2.62(m,1h),1.49(d,j=7.4hz,3h);13cnmr:(cdcl3,100mhz):δ143.7,141.0,137.8,135.7,131.3,129.8,128.7,127.9,127.5,127.0,126.9,126.8,25.1,16.3.hrms(ei)calculatedfor[c20h20si]+requiresm/z288.1334,foundm/z288.1334.iv-5:(s)-1-(4-甲氧基苯基)乙基苯硅烷(s)-(1-(4-methoxyphenyl)ethyl)(phenyl)silane油狀液體,84%yield,[α]20d=-19.5(c1.16,chcl3).99.4%ee,ir(cm-1):2954,2926,2136,1510,1247,1116.1hnmr(cdcl3,400mhz):δ7.43-7.35(m,3h),7.33-7.27(m,2h),7.01(d,j=8.8hz,2h),6.80(d,j=8.8hz,2h),4.33-4.28(m,2h),3.78(s,3h),2.59-2.51(m,1h),1.42(d,j=7.4hz,3h);13cnmr:(cdcl3,100mhz):δ157.2,136.5,135.6,131.5,129.7,127.9,127.8,113.8,55.2,24.2,16.7.hrms(ei)calculatedfor[c15h18osi]+requiresm/z242.1127,foundm/z242.1129.iv-6:(s)-1-(4-甲硫基苯基)乙基苯硅烷(s)-(1-(4-(methylthio)phenyl)ethyl)(phenyl)silane油狀液體,87%yield,[α]20d=-19.7(c1.26,chcl3).99.3%ee,ir(cm-1):2955,2922,2136,1492,1117.1hnmr(cdcl3,400mhz):δ7.44-7.35(m,3h),7.34-7.28(m,2h),7.17(d,j=8.0hz,2h),7.02(d,j=8.0hz,2h),4.33-4.29(m,2h),2.63-2.53(m,1h),2.46(s,3h),1.43(d,j=7.6hz,3h);13cnmr:(cdcl3,100mhz):δ141.7,135.6,134.2,131.1,129.7,127.8,127.6,127.3,24.9,16.4,16.3.hrms(ei)calculatedfor[c15h18ssi]+requiresm/z258.0898,foundm/z258.0896.iv-7:(s)-1-(4-氟苯基)乙基苯硅烷(s)-(1-(4-fluorophenyl)ethyl)(phenyl)silane油狀液體,83%yield,[α]20d=-15.5(c0.82,chcl3),99.0%ee,ir(cm-1):2955,2925,2138,1507,1229.1hnmr(cdcl3,400mhz):δ7.44-7.35(m,3h),7.35-7.27(m,2h),7.06-6.97(m,2h),6.97-6.88(m,2h),4.30(d,j=3.2hz,2h),2.66-2.54(m,1h),1.43(d,j=7.2hz,3h).13cnmr:(cdcl3,100mhz):δ160.7(d,j=241.4hz,1c),140.1(d,j=2.9hz,1c),135.6,131.1,129.8,128.3(d,j=7.3hz,1c),127.9,115.1(d,j=21.1hz,1c),24.6,16.6.19fnmr:(376.5mhz,cdcl3)δ-118.7;hrms(ei)calculatedfor[c14h15fsi]+requiresm/z230.0927,foundm/z230.0925.iv-8:(s)-1-(4-氯苯基)乙基苯硅烷(s)-(1-(4-chlorophenyl)ethyl)(phenyl)silane白色固體,86%yield,熔點(diǎn):41-42℃.[α]20d=-16.3(c1.12,chcl3),99.8%ee,ir(cm-1):2955,2924,2139,1490,1459.1hnmr(cdcl3,400mhz):δ7.42-7.36(m,3h),7.35-7.28(m,2h),7.20(d,j=8.0hz,2h),7.00(d,j=8.0hz,2h),4.30(d,j=3.2hz,2h),2.64-2.54(m,1h),1.43(d,j=7.6hz,3h);13cnmr:(cdcl3,100mhz):δ143.1,135.6,130.8,130.6,129.9,128.4,128.4,127.9,25.0,16.3.hrms(ei)calculatedfor[c14h15clsi]+requiresm/z246.0632,foundm/z246.0628.iv-9:(s)-1-(4-溴苯基)乙基苯硅烷(s)-(1-(4-bromophenyl)ethyl)(phenyl)silane油狀液體,83%yield,[α]20d=-14.8(c0.75,chcl3),99.4%ee,ir(cm-1):2955,2925,2138,1486,1458,1116.1hnmr(cdcl3,400mhz):δ7.43-7.28(m,7h),6.94(d,j=8.0hz,2h),4.30(d,j=3.2hz,2h),2.62-2.53(m,1h),1.43(d,j=7.6hz,3h);13cnmr:(cdcl3,100mhz):δ143.6,135.6,131.3,130.8,129.9,128.8,127.9,118.5,25.0,16.2.hrms(ei)calculatedfor[c14h15brsi]+requiresm/z290.0126,foundm/z290.0130.iv-10:(s)-1-(4-三氟甲基苯基)乙基苯硅烷(s)-phenyl(1-(4-(trifluoromethyl)phenyl)ethyl)silane油狀液體,83%yield,[α]20d=-9.9(c1.10,chcl3),98.9%ee,ir(cm-1):2957,2927,2141,1616,1327,1120.1hnmr(cdcl3,400mhz):δ7.48(d,j=8.0hz,2h),7.44-7.35(m,3h),7.35-7.28(m,2h),7.16(d,j=8.0hz,2h),4.32(d,j=2.8hz,2h),2.75-2.64(m,1h),1.47(d,j=7.2hz,3h);13cnmr:(cdcl3,100mhz):δ149.0,135.6,130.5,130.0,128.0,127.3,125.3,125.24,125.20,25.8,16.0;19fnmr:(376.5mhz,cdcl3)δ-62.2;hrms(esi)calculatedfor[c15h16f3si]+(m+h+)requiresm/z281.0973,foundm/z281.0967.iv-11:(s)-4-(1-苯硅基乙基)苯甲酸甲酯(s)-methyl4-(1-(phenylsilyl)ethyl)benzoate油狀液體,94%yield,[α]20d=-16.9(c1.08,chcl3),98.9%ee,ir(cm-1):2955,2925,2140,1724,1280.1hnmr(cdcl3,400mhz):δ7.97-7.87(m,2h),7.43-7.34(m,3h),7.34-7.27(m,2h),7.12(d,j=8.0hz,2h),4.32(d,j=3.2hz,2h),3.90(s,3h),2.76-2.64(m,1h),1.47(d,j=7.2hz,3h);13cnmr:(cdcl3,100mhz):δ167.2,150.4,135.6,130.6,130.0,129.7,127.9,127.0,126.9,51.9,26.1,15.9;hrms(esi)calculatedfor[c16h19o2si]+(m+h+)requiresm/z271.1154,foundm/z271.1163.iv-12:(s)-4-(1-苯硅基乙基)乙酸芐酯(s)-4-(1-(phenylsilyl)ethyl)benzylacetate油狀液體,86%yield,[α]20d=-15.6(c1.12,chcl3),99.5%ee,ir(cm-1):2956,2924,2137,1741,1231.1hnmr(cdcl3,400mhz):δ7.46-7.36(m,3h),7.35-7.28(m,2h),7.24(d,j=8.4hz,2h),7.09(d,j=8.0hz,2h),5.06(s,2h),4.37-4.26(m,2h),2.69-2.57(m,1h),2.10(s,3h),1.44(d,j=7.6hz,3h);13cnmr:(cdcl3,100mhz):δ170.8,144.8,135.5,132.5,131.1,129.7,128.5,127.8,127.2,66.1,25.1,20.9,16.3;hrms(esi)calculatedfor[c17h21o2si]+(m+h+)requiresm/z285.1311,foundm/z285.1310.iv-13:(s)-1-(4-(2-甲基-1,3-二氧環(huán)戊基-2-)苯基)乙基苯硅烷(s)-(1-(4-(2-methyl-1,3-dioxolan-2-yl)phenyl)ethyl)(phenyl)silane白色固體,94%yield,熔點(diǎn):90-92℃.[α]20d=-14.3(c0.97,chcl3),99.0%ee,ir(cm-1):2955,2925,2136,1459,1374.1hnmr(cdcl3,400mhz):δ7.49-7.27(m,7h),7.07(d,j=8.0hz,2h),4.40-4.25(m,2h),4.13-3.95(m,2h),3.88-3.72(m,2h),2.70-2.55(m,1h),1.65(s,3h),1.44(d,j=7.6hz,3h);13cnmr:(cdcl3,100mhz):δ144.1,135.6,131.3,129.7,127.8,126.8,125.3,108.8,64.4,27.5,25.0,16.3;hrms(ei)calculatedfor[c18h22o2si]+requiresm/z298.1389,foundm/z298.1389.iv-14:(s)-1-(3-三氟甲基苯基)乙基苯硅烷(s)-phenyl(1-(3-(trifluoromethyl)phenyl)ethyl)silane油狀液體,84%yield,[α]20d=-10.5(c1.31,chcl3),98.8%ee,ir(cm-1):2956,2926,2140,1447,1330.1hnmr(cdcl3,400mhz):δ7.44-7.21(m,9h),4.32(d,j=2.8hz,2h),2.74-2.63(m,1h),1.47(d,j=7.2hz,3h);13cnmr:(cdcl3,100mhz):δ145.6,135.6,130.5,130.4,130.0,128.7,128.0,123.8,123.7,121.9,121.8,25.7,16.0;19fnmr:(376.5mhz,cdcl3)δ-62.6;hrms(esi)calculatedfor[c15h16f3si]+(m+h+)requiresm/z281.0973,foundm/z281.0980.iv-15:(s)-1-(3-氯苯基)乙基苯硅烷(s)-(1-(3-chlorophenyl)ethyl)(phenyl)silane油狀液體,74%yield,[α]20d=-20.5(c1.10,chcl3),98.6%ee,ir(cm-1):2956,2140,1593,1476,1427.1hnmr(cdcl3,400mhz):δ7.45-7.36(m,3h),7.36-7.28(m,2h),7.16(dd,j=7.6,7.6hz,1h),7.12-7.02(m,2h),6.94(d,j=7.6hz,1h),4.31(d,j=2.8hz,2h),2.67-2.53(m,1h),1.43(d,j=7.6hz,3h);13cnmr:(cdcl3,100mhz):δ146.8,135.6,134.2,130.7,129.9,129.5,127.9,127.1,125.3,125.2,25.4,16.1;hrms(ei)calculatedfor[c14h15clsi]+requiresm/z246.0632,foundm/z246.0634.iv-16:(s)-1-間甲苯基乙基苯硅烷(s)-phenyl(1-(m-tolyl)ethyl)silane油狀液體,76%yield,[α]20d=-20.1(c1.07,chcl3),99.4%ee,ir(cm-1):2955,2924,2136,1604,1430.1hnmr(cdcl3,400mhz):δ7.44-7.35(m,3h),7.34-7.28(m,2h),7.17-7.11(m,1h),6.96-6.87(m,3h),4.34-4.28(m,2h),2.62-2.53(m,1h),2.29(s,3h),1.44(d,j=7.4hz,3h);13cnmr:(cdcl3,100mhz):δ144.5,137.8,135.6,131.5,129.7,128.2,127.9,127.8,125.8,124.1,25.2,21.4,16.4.hrms(ei)calculatedfor[c15h18si]+requiresm/z226.1178,foundm/z226.1178.iv-17:(s)-1-鄰甲苯基乙基苯硅烷(s)-phenyl(1-(o-tolyl)ethyl)silane油狀液體,62%yield,[α]20d=+32.8(c0.89,chcl3),99.8%ee,ir(cm-1):3017,2955,2925,2136,1459.1hnmr(cdcl3,400mhz):δ7.43-7.36(m,3h),7.34-7.28(m,2h),7.19-7.13(m,1h),7.10(d,j=7.6hz,2h),7.07-7.01(m,1h),4.32-4.25(m,2h),2.82-2.73(m,1h),2.20(s,3h),1.45(d,j=7.6hz,3h);13cnmr:(cdcl3,100mhz):δ142.8,135.6,134.8,131.6,130.1,129.7,127.8,126.2,126.0,124.8,20.8,20.0,16.6.hrms(ei)calculatedfor[c15h18si]+requiresm/z226.1178,foundm/z226.1181.iv-18:(s)-1-(3-甲氧基-4-氟苯基)乙基苯硅烷(s)-(1-(4-fluoro-3-methoxyphenyl)ethyl)(phenyl)silane油狀液體,87%yield,[α]20d=-18.3(c1.07,chcl3),99.4%ee,ir(cm-1):3069,2136,1607,1515,1416,1276.1hnmr(cdcl3,400mhz):δ7.48-7.36(m,3h),7.36-7.28(m,2h),6.94(dd,j=8.4,11.2hz,1h),6.66-6.52(m,2h),4.40-4.25(m,2h),3.74(s,3h),2.65-2.51(m,1h),1.44(d,j=7.6hz,3h);13cnmr:(cdcl3,100mhz):δ150.2(d,j=241.3hz,1c),147.1(d,j=10.9hz,1c),140.7(d,j=3.7hz,1c),135.6,131.1,129.8,127.9,118.7(d,j=6.5hz,1c),115.7(d,j=17.5hz,1c),112.4,55.9,25.1,16.4;19fnmr:(376.5mhz,cdcl3)δ-140.6;hrms(ei)calculatedfor[c15h17fosi]+requiresm/z260.1033,foundm/z260.1035.iv-19:(s)-1-(萘基-1-)乙基苯硅烷(s)-(1-(naphthalen-1-yl)ethyl)(phenyl)silane油狀液體,83%yield,[α]20d=+148(c0.89,chcl3),98.1%ee,ir(cm-1):2955,2924,2139,1510,1460.1hnmr(cdcl3,400mhz):δ8.10-8.02(m,1h),7.90-7.80(m,1h),7.66(d,j=8.0hz,1h),7.53-7.34(m,6h),7.33-7.21(m,3h),4.47-4.31(m,2h),3.50-3.39(m,1h),1.59(d,j=7.2hz,3h);13cnmr:(cdcl3,100mhz):δ140.8,135.6,133.9,131.4,131.1,129.7,128.9,127.8,125.6,125.5,125.3,123.4,123.2,20.0,16.8;hrms(esi)calculatedfor[c18h19si]+(m+h+)requiresm/z263.1256,foundm/z263.1255.iv-20:(s)-1-(萘基-2-)乙基苯硅烷(s)-(1-(naphthalen-2-yl)ethyl)(phenyl)silane白色固體,85%yield,熔點(diǎn):56-58℃.[α]20d=-46.8(c0.98,chcl3),98.8%ee,ir(cm-1):2956,2923,2137,1598,1462.1hnmr(cdcl3,400mhz):δ7.82-7.69(m,3h),7.50(s,1h),7.46-7.35(m,5h),7.33-7.22(m,3h),4.41-4.33(m,2h),2.83-2.74(m,1h),1.55(d,j=7.6hz,3h);13cnmr:(cdcl3,100mhz):δ142.2,135.7,133.8,131.6,131.3,129.8,127.9,127.8,127.6,127.3,126.7,125.9,124.8,124.5,25.7,16.4.hrms(ei)calculatedfor[c18h18si]+requiresm/z262.1178,foundm/z262.1182.iv-21:(s)-1-甲基-5-(1-苯硅基乙基)-吲哚(s)-1-methyl-5-(1-(phenylsilyl)ethyl)-1h-indole油狀液體,68%yield,[α]20d=-38.0(c0.50,chcl3).99.2%ee,ir(cm-1):2953,2924,2868,2132,1513,1488.1hnmr(cdcl3,400mhz):δ7.47-7.43(m,2h),7.40-7.34(m,2h),7.33-7.27(m,2h),7.21(d,j=8.4hz,1h),7.03-6.98(m,2h),6.39(d,j=3.2hz,1h),4.38-4.32(m,2h),3.76(s,3h),2.74-2.66(m,1h),1.50(d,j=7.6hz,3h);13cnmr:(cdcl3,100mhz):δ135.6,135.3,135.0,132.1,129.5,128.8,127.8,121.7,118.5,109.0,100.4,32.7,24.9,17.4.hrms(ei)calculatedfor[c17h19nsi]+requiresm/z265.1287,foundm/z265.1290.iv-22:(s)-1-(噻吩基-2-)乙基苯硅烷(s)-phenyl(1-(thiophen-2-yl)ethyl)silane油狀液體,77%yield,[α]20d=-4.6(c1.21,toluene),98.0%ee,ir(cm-1):2956,2925,2867,2140,1457,1431.1hnmr:(cdcl3,400mhz)δ7.48-7.43(m,2h),7.41-7.37(m,1h),7.36-7.29(m,2h),7.05(dd,j=5.0,1.0hz,1h),6.90(dd,j=5.2,3.6hz,1h),6.71-6.65(m,1h),4.45-4.35(m,2h),2.95-2.85(m,1h),1.49(d,j=7.6hz,3h);13cnmr:(cdcl3,100mhz):δ148.4,135.6,130.9,129.9,127.9,126.8,122.3,121.9,20.7,18.0.hrms(ei)calculatedfor[c12h14ssi]+requiresm/z218.0585,foundm/z218.0585.iv-23:(s)-1-(苯并噻吩基-3-)乙基苯硅烷(s)-(1-(benzo[b]thiophen-3-yl)ethyl)(phenyl)silane油狀液體,72%yield,[α]20d=+150.6(c1.07,chcl3),98.5%ee,ir(cm-1):2955,2924,2868,2140,1458,1428.1hnmr(cdcl3,400mhz):δ7.89-7.82(m,1h),7.76-7.69(m,1h),7.45-7.27(m,7h),6.89(s,1h),4.46-4.32(m,2h),3.07-2.96(m,1h),1.54(d,j=7.2hz,3h);13cnmr:(cdcl3,100mhz):δ140.4,139.1,138.3,135.7,131.0,129.8,127.9,124.2,123.6,122.8,121.9,119.0,18.7,16.3;hrms(esi)calculatedfor[c16h16ssina]+(m+na+)requiresm/z291.0640,foundm/z291.0644.iv-24:(s)-2-甲氧基-5-(1-(苯硅基)乙基)吡啶(s)-2-methoxy-5-(1-(phenylsilyl)ethyl)pyridine油狀液體,74%yield,[α]20d=-12.2(c1.20,chcl3),99.0%ee,ir(cm-1):2925,2869,2136,1604,1491.1hnmr(cdcl3,400mhz):δ7.90(d,j=2.4hz,1h),7.45-7.36(m,3h),7.35-7.24(m,3h),6.64(d,j=8.4hz,1h),4.32(d,j=3.2hz,2h),3.90(s,3h),2.59-2.49(m,1h),1.43(d,j=7.6hz,3h);13cnmr:(cdcl3,100mhz):δ162.1,144.7,137.4,135.4,132.3,130.6,129.8,127.9,110.3,53.0,21.4,16.4;hrms(ei)calculatedfor[c14h17nosi]+requiresm/z243.1079,foundm/z243.1077.iv-25:(s)-(正辛基-2-)苯硅烷(s)-octan-2-yl(phenyl)silane油狀液體,91%yield,[α]20d=+5.8(c1.06,chcl3).84.9%ee,ir(cm-1):2956,2924,2855,2131,1462,1430.1hnmr(cdcl3,400mhz):δ7.56(dd,j=1.6,7.6hz,2h),7.42-7.32(m,3h),4.25-4.16(m,2h),1.52-1.38(m,2h),1.35-1.20(m,8h),1.18-1.09(m,1h),1.05(d,j=6.6hz,3h),0.87(t,j=6.6hz,3h);13cnmr:(cdcl3,100mhz):δ135.6,132.3,129.4,127.9,33.5,31.8,29.4,28.5,22.7,16.3,16.1,14.1.hrms(ei)calculatedfor[c14h24si]+requiresm/z220.1647,foundm/z220.1646.iv-26:(s)-((5-溴正戊基)-2-)苯硅烷(s)-(5-bromopentan-2-yl)(phenyl)silane油狀液體,53%yield,[α]20d=+2.6(c1.13,toluene),84.7%ee,ir(cm-1):2925,2853,2133,1460,1377.1hnmr(cdcl3,400mhz):δ7.62-7.51(m,2h),7.47-7.31(m,3h),4.35-4.12(m,2h),3.49-3.25(m,2h),2.10-1.80(m,2h),1.73-1.59(m,1h),1.52-1.38(m,1h),1.24-1.00(m,4h);13cnmr:(cdcl3,100mhz):δ135.6,131.5,129.6,127.9,33.6,31.9,31.7,15.9,15.6;hrms(esi)calculatedfor[c11h18brsi]+(m+h+)requiresm/z257.0361,foundm/z257.0362.iv-27:(s)-2-(10-(苯硅基)十一烷基)異吲哚-1,3-二酮(s)-2-(10-(phenylsilyl)undecyl)isoindoline-1,3-dione油狀液體,89%yield,opticalrotation:[α]20d=+2.9(c0.78,chcl3),80.8%ee,ir(cm-1):2925,2854,2129,1715,1396.1hnmr(cdcl3,400mhz):δ7.84(dd,j=3.2,5.2hz,2h),7.70(dd,j=2.8,5.2hz,2h),7.61-7.50(m,2h),7.43-7.30(m,3h),4.30-4.10(m,2h),3.67(t,j=7.2hz,2h),1.77-1.60(m,2h),1.45-1.17(m,14h),1.17-1.00(m,4h);13cnmr:(cdcl3,100mhz):δ168.3,135.5,133.7,132.14,132.11,129.3,127.8,123.0,38.0,33.4,29.5,29.4,29.1,28.5,28.4,26.8,16.2,16.1;hrms(ei)calculatedfor[c25h33no2si]+requiresm/z407.2281,foundm/z407.2280.iv-28:(s)-5-苯硅基己基-1-醇(s)-5-(phenylsilyl)hexan-1-ol油狀液體,77%yield,opticalrotation:[α]20d=+4.7(c1.24,chcl3),81.3%ee,ir(cm-1):3359,2926,2862,2128,1459,1429.1hnmr(cdcl3,400mhz):δ7.56(d,j=7.6hz,2h),7.43-7.31(m,3h),4.26-4.17(m,2h),3.61(t,j=6.4hz,2h),1.64-1.46(m,4h),1.42-1.31(m,2h),1.28-1.20(m,1h),1.20-1.10(m,1h),1.07(d,j=6.8hz,3h);13cnmr:(cdcl3,100mhz):δ135.5,131.9,129.4,127.8,77.3,77.0,76.7,62.6,33.1,32.6,24.6,16.2,16.0;hrms(ei)calculatedfor[c12h20osi–h2]+requiresm/z206.1127,foundm/z206.1125.iv-29:(s)-5-苯硅基己基-2-酮(s)-5-(phenylsilyl)hexan-2-one油狀液體,81%yield,opticalrotation:[α]20d=+4.2(c1.10,chcl3),82.6%ee,ir(cm-1):2924,2866,2130,1716,1458,1429.1hnmr(cdcl3,400mhz):δ7.59-7.53(m,2h),7.44-7.33(m,3h),4.27-4.18(m,2h),2.60-2.39(m,2h),2.10(s,3h),1.87-1.76(m,1h),1.67-1.54(m,1h),1.20-1.09(m,1h),1.07(d,j=6.8hz,3h);13cnmr:(cdcl3,100mhz):δ208.4,135.4,131.2,129.5,127.8,77.3,77.0,76.7,42.3,29.6,27.1,15.7,15.6;hrms(ei)calculatedfor[c12h18osi]+requiresm/z206.1127,foundm/z206.1129.iv-30:(s)-(對(duì)甲氧基苯基)(1-苯基乙基)硅烷(s)-(4-methoxyphenyl)(1-phenylethyl)silane油狀液體,97%yield,[α]20d=-16.1(c1.04,chcl3),99.5%ee,ir(cm-1):2955,2924,2134,1596,1377,1115.1hnmr(cdcl3,400mhz):δ7.31(d,j=8.4hz,2h),7.27-7.21(m,2h),7.14-7.06(m,3h),6.85(d,j=8.4hz,2h),4.30(d,j=3.2hz,2h),3.80(s,3h),2.62-2.53(m,1h),1.44(d,j=7.6hz,3h);13cnmr:(cdcl3,100mhz):δ161.0,144.7,137.2,128.3,127.1,124.9,122.0,113.7,55.0,25.6,16.3.hrms(ei)calculatedfor[c15h18osi]+requiresm/z242.1127,foundm/z242.1126.iv-31:(s)-(對(duì)氯苯基)(1-苯基乙基)硅烷(s)-(4-chlorophenyl)(1-phenylethyl)silane油狀液體,80%yield,[α]20d=-19.3(c0.95,chcl3),99.4%ee,ir(cm-1):2956,2924,2855,2141,1580,1461.1hnmr(cdcl3,400mhz):δ7.31-7.21(m,6h),7.15-7.10(m,1h),7.06(d,j=7.6hz,2h),4.31(d,j=3.2hz,2h),2.64-2.55(m,1h),1.44(d,j=7.6hz,3h);13cnmr:(cdcl3,100mhz):δ144.1,136.9,136.2,129.6,128.4,128.1,127.1,125.2,25.3,16.2.hrms(ei)calculatedfor[c14h15clsi]+requiresm/z246.0632,foundm/z246.0632.實(shí)施例2:產(chǎn)物氧化合成手性醇類化合物(應(yīng)用實(shí)例)20ml反應(yīng)管中,加入1a(0.087g,0.3mmol)、二氯甲烷(15ml),0℃下攪拌并加入hbf4·et2o(0.35g,1.6mmol,40%wt).攪拌3h,旋去溶劑,然后按順序加入四氫呋喃(3ml),甲醇(3ml),氟化鉀(0.07g,1.2mmol),碳酸氫鉀(0.30g,3.0mmol),h2o2(1.5ml,30%wt).室溫?cái)嚢?5h,加水稀釋,乙醚萃取3次,飽和食鹽水洗滌,無水硫酸鈉干燥,旋干,pe/etoac=4/1過柱得到0.048g(0.24mmol,81%yield)目標(biāo)產(chǎn)物。白色固體,[α]20d=-42(c0.27,chcl3),99%ee,1hnmr(cdcl3,400mhz):δ7.55-7.61(m,4h),7.40-7.47(m,4h),7.31-7.37(m,1h),4.95(q,j=6.4hz,1h),1.86(br,1h),1.54(d,j=6.4hz,3h).(實(shí)驗(yàn)步驟參考文獻(xiàn):bergens,s.h.;noheda,p.;whelan,j.;bosnich,b.j.am.chem.soc.1992,114,2121-2128.化合物數(shù)據(jù)與文獻(xiàn)一致:salvi,n.a.;chattopadhyay,s.tetrahedron.2001,57,2833–2839.)取實(shí)施例1的合成產(chǎn)物參照上述方法氧化成手性醇類化合物,結(jié)果如下表1所示:表1實(shí)施例3:產(chǎn)物氧化合成硅醇類化合物(應(yīng)用實(shí)例)20ml反應(yīng)管中加入2a(0.1046g,0.5mmol),bcl3(0.5mmol,0.5ml,1.0mindcm),h2o(1.2ml)、二氯甲烷(2.0ml).攪拌過夜,加水稀釋,二氯甲烷萃取3次,飽和食鹽水洗滌,無水硫酸鈉干燥。pe/etoac=10/1過柱得到0.0790g(0.35mmol,70%yield)目標(biāo)產(chǎn)物。油狀液體,1:1dr.1hnmr(cdcl3,400mhz):δ7.45-7.51(m,2h),7.19-7.44(m,12h),7.03-7.15(m,6h),4.93(d,j=1.8hz,1h),4.90(d,j=2.4hz,1h),2.48-2.57(m,2h),2.17(br,2h),1.41(d,j=7.8hz,3h),1.38(d,j=7.8hz,3h).(化合物數(shù)據(jù)與文獻(xiàn)一致:visco,m.d.;wieting,j.m.;mattson,a.e.org.lett.2016,18,2883-2885.)實(shí)施例4:產(chǎn)物氧化合成手性硅醇類化合物(應(yīng)用實(shí)例)20ml反應(yīng)管中加入3a(0.13g,0.62mmol),pd/c(0.062g,0.06mmol),h2o(0.2ml)、et2o(2.0ml)。攪拌過夜,過濾,濾液加水稀釋,乙醚萃取3次,飽和食鹽水洗滌,無水硫酸鈉干燥。pe/etoac=1/1過柱得到0.14g(0.57mmol,92%yield)目標(biāo)產(chǎn)物。白色固體.熔點(diǎn):120-122℃.[α]20d=-17.0(c0.44,chcl3),99%ee,ir(cm-1):3315,1597,1491,1455,1430,1379,1123.1hnmr(cdcl3,400mhz):δ7.55(d,j=7.6hz,2h),7.39-7.47(m,1h),7.35(t,j=7.6hz,2h),7.20-7.29(m,2h),7.08-7.18(m,3h),2.79(br,2h),2.49(q,j=7.6hz,1h),1.41(d,j=7.6hz,3h);13cnmr:(cdcl3,100mhz):δ143.3,134.3,133.4,130.4,128.5,127.8,127.5,125.1,28.9,14.5.hrms(ei)calculatedfor[c14h16o2si]+requiresm/z244.0920,foundm/z244.0918.(實(shí)驗(yàn)步驟參考文獻(xiàn):visco,m.d.;wieting,j.m.;mattson,a.e.org.lett.2016,18,2883-2885.)20ml反應(yīng)管中加入4a(0.16g,0.69mmol),pd/c(0.073g,0.068mmol),h2o(0.2ml)、et2o(2.0ml)。攪拌過夜,過濾,濾液加水稀釋,乙醚萃取3次,飽和食鹽水洗滌,無水硫酸鈉干燥。pe/etoac=1/1過柱得到0.12g(0.46mmol,67%yield)目標(biāo)產(chǎn)物。白色固體.熔點(diǎn):111-113℃.[α]20d=-13.0(c0.94,chcl3),99%ee,ir(cm-1):3337,2958,2922,1599,1508.1hnmr(cdcl3,400mhz):δ7.57-7.50(m,2h),7.47-7.40(m,1h),7.39-7.32(m,2h),7.12-7.04(m,2h),6.98-6.90(m,2h),2.53-2.43(m,3h),1.41(d,j=7.6hz,3h);13cnmr:(cdcl3,100mhz):δ162.8,138.8,134.3,133.1,130.5,128.8,127.8,115.0,28.0,14.7;19fnmr:(376.5mhz,cdcl3)δ-118.6;hrms(ei)calculatedfor[c14h15fo2si]+requiresm/z262.0825,foundm/z262.0827.(實(shí)驗(yàn)步驟參考文獻(xiàn):visco,m.d.;wieting,j.m.;mattson,a.e.org.lett.2016,18,2883-2885.)20ml反應(yīng)管中加入5a(0.17g,0.77mmol),pd/c(0.086g,0.081mmol),h2o(0.2ml)、et2o(2.0ml)。攪拌過夜,過濾,濾液加水稀釋,乙醚萃取3次,飽和食鹽水洗滌,無水硫酸鈉干燥。pe/etoac=1/1過柱得到0.13g(0.53mmol,69%yield)目標(biāo)產(chǎn)物。白色固體.熔點(diǎn):52-54℃.[α]20d=-6.4(c1.18,chcl3),85%ee,ir(cm-1):3351,2956,2924,2854,1462,1378.1hnmr(cdcl3,400mhz):δ7.68-7.60(m,2h),7.48-7.32(m,3h),2.83-2.54(m,2h),1.66-1.51(m,1h),1.49-1.35(m,1h),1.33-1.13(m,8h),1.02(s,4h),0.86(t,j=6.8hz,3h);13cnmr:(cdcl3,100mhz):δ134.5,134.2,130.0,127.7,31.9,30.6,29.3,28.3,22.7,19.1,14.1,13.2;hrms(ei)calculatedfor[c14h24o2si-c6h6]+requiresm/z174.1076,foundm/z174.1078.(實(shí)驗(yàn)步驟參考文獻(xiàn):visco,m.d.;wieting,j.m.;mattson,a.e.org.lett.2016,18,2883-2885.)實(shí)施例5:產(chǎn)物合成多取代硅烷化合物(應(yīng)用實(shí)例)干燥的20ml的反應(yīng)管中,加入苯乙烯(63μl,0.5mmol),6a(0.0682g,0.32mmol),iproip-fecl2(0.0133g,0.025mmol),nabhet3(75μl,0.075mmol),反應(yīng)12小時(shí),pe/etoac(50:1―20:1)過柱得到0.0795g(0.25mmol,78%yield,2.7:1dr)。目標(biāo)產(chǎn)物,油狀液體.ir(cm-1):3024,2925,2114,1600,1492,1452.1hnmr(400mhz,cdcl3):δ7.48-7.41(m,1.51h),7.41-7.28(m,3.51h),7.26-7.16(m,4h),7.15-7.00(m,5.57h),7.00-6.95(m,0.57h),4.35-4.30(m,0.28h),4.30-4.23(m,0.72h),2.63-2.39(m,3h),1.40(d,j=7.6hz,0.84h),1.37(d,j=7.6hz,2.20h),1.22-1.14(m,0.59h),1.14-1.05(m,1.49h);hrms(ei)calculatedfor[c22h24si]+requiresm/z316.1647,foundm/z316.1647.(實(shí)驗(yàn)步驟參考文獻(xiàn):chen,j.h.;cheng,b.;cao,m.y.;lu,z.angew.chem.int.ed.2015,54,4661–4664.)實(shí)施例6:產(chǎn)物合成多取代硅烷化合物(應(yīng)用實(shí)例)干燥的20ml的反應(yīng)管中,加入苯乙炔(110μl,1.0mmol),7a(0.11g,0.53mmol),xantphos-cobr2(xantphos與cobr2形成的金屬絡(luò)合物)(0.041g,0.052mmol),nabhet3(150μl,0.15mmol),反應(yīng)5小時(shí),pe過柱得到0.097g(0.31mmol,59%yield,2.7:1dr)目標(biāo)產(chǎn)物,油狀液體.ir(cm-1):2955,2925,2119,1600,1493.1hnmr(cdcl3,400mhz):δ7.50-7.26(m,10h),7.24-7.17(m,2h),7.15-7.03(m,3h),7.02-6.98(m,0.36h),6.92(d,j=19.2hz,0.70h),6.53(dd,j=3.6,18.8hz,0.26h),6.38(dd,j=3.6,19.2hz,0.69h),4.62(dd,j=2.8,3.2hz,1.0h),2.73-2.61(m,1h),1.51-1.42(m,3h);hrms(ei)calculatedfor[c22h22si]+requiresm/z314.1491,foundm/z314.1487.(實(shí)驗(yàn)步驟參考文獻(xiàn):guo,j.;lu,z.angew.chem.int.ed.2016,55,10835-10838.)實(shí)施例7:產(chǎn)物合成多取代硅烷化合物(應(yīng)用實(shí)例)干燥的20ml的反應(yīng)管中,加入苯乙炔(66μl,0.6mmol),8a(0.11g,0.53mmol),2,4-dmboip·cobr2(0.015g,0.025mmol),nabhet3(75μl,0.075mmol),反應(yīng)3小時(shí),pe過柱得到0.10g(0.33mmol,63%yield,2.7:1dr)目標(biāo)產(chǎn)物,油狀液體.ir(cm-1):2956,2925,2125,1599,1492.1hnmr(cdcl3,400mhz,):δ7.57-7.27(m,6h),7.24-6.95(m,9h),6.17(d,j=2.0hz,0.25h),6.01(d,j=2.4hz,0.69h),5.75(d,j=2.4hz,0.25h),5.65(d,j=2.4hz,0.69h),4.77(d,j=3.6hz,1h),2.73-2.63(m,1h),1.44(d,j=7.6hz,0.85h),1.39(d,j=7.6hz,2.13h);hrms(ei)calculatedfor[c22h22si]+requiresm/z314.1491,foundm/z314.1494.(實(shí)驗(yàn)步驟參考文獻(xiàn):guo,j.;lu,z.angew.chem.int.ed.2016,55,10835-10838.)實(shí)施例8不同催化劑催化效率和選擇性室溫下,氮?dú)獗Wo(hù)下,在一干燥的反應(yīng)試管中加入手性cox2-oip絡(luò)合物(0.05mmol),苯乙烯(1.2mmol),苯基硅烷(1.0mmol),thf(4ml),叔丁醇鈉(0.15mmol),然后在室溫?cái)嚢?小時(shí)后停止反應(yīng),通過均三甲苯作內(nèi)標(biāo)計(jì)算1和2的核磁產(chǎn)率,通過高效液相色譜測(cè)1的ee值。反應(yīng)式中,1為手性產(chǎn)物,2為非手性副產(chǎn)物,不同催化劑的選擇性如下。手性cox2-oip絡(luò)合物催化劑和產(chǎn)物情況如下表2所示表2entryr9r11r13r8nmryieldof1nmryieldof2eeof11mehmeipr693.672.22iprhipripr695.488.23-chph2me-chph2ipr593.998.64-chph2cl-chph2ipr541.698.85-chph2-ome-chph2ipr632.898.76-chph2-ome-chph2bn701.298.57-chph2-ome-chph2tbu6.312--8-chph2-ome-chph2me741.297.9從表2可以看出,催化劑6的目標(biāo)手性產(chǎn)物收率最高,非手性副產(chǎn)物收率最低,因此選用催化劑6為最優(yōu)催化劑,實(shí)施例1均以催化劑6進(jìn)行合成。催化劑參照參考文獻(xiàn):guo,j.;shen,x.z.;lu,z.angew.chem.int.ed.2017,56,615-618.合成,催化劑1、2為已公開化合物,催化劑3-8的產(chǎn)物分析數(shù)據(jù)如下:催化劑3綠色粉末.anal.calcdforc46h43cl2con3o+1.5h2o:c,68.15;h,5.72;n,5.18;found:c,68.37;h,5.56;n,5.09.催化劑5綠色粉末.anal.calcdforc46h43cl2con3o2+2h2o:c,66.11;h,5.67;n,5.03;found:c,66.35;h,5.39;n,5.39.催化劑4綠色粉末.anal.calcdforc45h40cl3con3o+2h2o:c,64.33;h,5.28;n,5.00;found:c,64.49;h,5.06;n,4.90.催化劑8棕色粉末.anal.calcdforc44h39cl2con3o2+2h2o:c,65.43;h,5.37;n,5.20;found:c,65.67;h,5.14;n,5.14.催化劑7綠色粉末.anal.calcdforc47h45cl2con3o2+2h2o:c,66.43;h,5.81;n,4.95;found:c,66.53;h,5.72;n,4.72.當(dāng)前第1頁12