半稳定磷叶立德和亚胺高选择性合成卤代烯烃.docx

1、Vol.33iNo.3Mar.j2021化学聆与应用ChemicaResearchandApplication攵章辨号226008；.嘛I香A口成肝»喊Sr妣L麻良由MftIKBffl'七iiJSj荷'z协耕辜i1WMitt婀枷招厂只应、：Is度反黄诬玳O不r除肾麻定！倦WAt4-,r-x、»tzm蜩户堆'二q'H一:械W甥挪族成中关中?-?-Ahuo10041656U021J03053209Stereoselectivesynthesisofdisubstitutedalkenylhalidesviasemistabilizedtriphe

2、nylphosphoniumYlide$withiminesDONGDejun1jXUYifu2,YANGZhanping'iLIANGYinchun11.Nmtong!ZhuhaiiKunmingCelluloseFibersCompanyTechnicalCenlerjNantong2260O8iChina；2.NantongCeJuloseFibersCompnyjNantong226008(China)Abstract!Abro>drangeolN$ulfonylaromaticiheleroaromilic?8lph”betaunsaluraiediandaliphat

3、:ciminesreacledw:1b$emis:abilizedphosphoniumylide$toiffordanirrayofbothl.zlnd!e!isomersofalkenylbromidesingoodyieldsandwilhgreaterthan99:Istereoseleclivity.Moreover!thistunableprotocolhadbeensuccessfullyappliedtothehighlyslereoselectivesynthesisofalkenylchloridejandalkenyliodide$.Theolelinalionreact

4、ioncou.dpoienlidlyproceedthroughaWiltigtypereaclionpathwayinrolvingiormal2i2cycloaddliontogeneratea112iuphospheuneintermediatefollowedbyeliminalionofanim:nophosphoraneyieldinganalkene,whereintheNsulfonrlgroupsserveaspowerlulkindlesIofinelyluneslereoselectirily.Keywords!imines!semjiabiHzedphosphonium

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9、lo!,mi4H,I1748-737I,mi2H)j716(diJ=8IHzj1H)1646I.djJ=81H”1H)；13CNMR(75MHziCDChj16：1367i1333j1322j1284j128ij12791127811263)1262|1260i1259j106601yellowoil；*HNMR1300RrMHziCDC1J?6：147-142),mi2H)i735725I.mi3H)j715-704I,m?1H)1688672'm,2H)162QIdjJ二72Hzi1H)；，5CNMR(75MHzjCDClJj&1365?136Oj1326?1285i128

10、Ij4Zlldj乂/曲yellowoil；*HNMR(300MHijCDC1Jj5：823(djJ=90Hzj2H,1j783hiJ=9QHzj2H.)j716l.djJ=8l.Hz?1H)1668IdiJ=81Hzj1H)；13CNMR(75MHz,CDCIs)j6：1412i1304,1285i1234|110h1266?1242i1083o4Zsllj)jyellowoil；lHNMR(300RrMHziCDC3J,6：727-715(mi5H.I1615-604Im'|2H)1277(-267I,m?2H.)p257247(mi2H/；13CNMRU5MHziCDCI)15：1

11、41Oj1308j1285,128126li1187o4Zllei1yellowoil；NMR1300BrJI6：785/80m1H/J7/43-737mi1Hh73D723(mi3H/j659UiJ=81MHzjCDCI3ImiIHli7辱分村舛晶I招2舟E15：1335?4Z11ki1yellowoil；1HNMR(300MHijCDCI3i16：588-573im,2H),2232,14Im-2H)j155126Im?8H.)1095-085Imi3h|；，JCNMR1.75MHzjCDCI3)j6：1282i1197,316j296j26226Ij227)14lo10934Zllfjy

12、ellowoil；*HNMRI300、子NBrMHziCDClj)16：865862Imi1H)i806-801!.mi1H)j776-769Imj1H)i729-719I,mi2H)?667UJ=81Hzj1H)；l3CNMR1J5MHzjCDChii6：1544j1495j1360?1332i1237j4Zllljyellowoil；'HMHziCDCLh6：603UiJ=7578!,mj1H)j260-250(mjI,mi1OH/；13CNMR(75MHijNMR1H)15843002Hzj1H)11451CDCI3)j6：HO10Ij1228jl09h4Zllgjyellowo

13、il：'HNMRI.300MHzjCDCh)16；7N724l.mj3H)j708703i,mi1H)j631(diJ=81Hzj1H)；11CNMR(75MHz?CDClJi6：1382|1305j127Oj1235j1054,3881315i258125604Zllmiph/=(yellowoil；lHNMRI.300MHz?CDChij6：735725Imi5H),662I,djJ=84Hzi1H)1625Id?J=84Hzi1H)；lJCNMR(75MHzjCDCh)16：1333,1322>1292j12881110801261,11?6c4Zim顷Howoil；

14、9;HNMRIj00ClMHz?CDClJj6：745740(mi2H)j731-721Imi3"716711mi1H,1j657(d?J=153Hzj1H)j646-638Imj1H)j603IdjJ=72Hzi第期戳,等:1H):,JCNMR(75MHzjCDCI：)i6：1355?1329)13。Oj1287j1265j1264j1245)1176o4ZI1ojyellowoiHNMRLooMHijCDCI3i16：720-712l.mj2H.I1601(diJ=5,4Hzi1H)j579-,572!mj1H),27,4-265!,mi2H)1258250Imi2H)；13CN

15、MR1.75MHziCDClJj5：HO%13。7?1285j1284j1260i1300MHziCDCIJJ5：730-716Imj4H/j701Id?J=141Hzj1h!?667(diJ=141Hz?1Hl；UCNMRU5MHziCDC,h6：136li134li134Oj129I?1274il072o1187j345i287c4Zllpjnllowoil；1HNMR(300MH”CDClJ16：764-160I,mi1H)j741-723Imj5H)1656UJ=87Hz?1H)；13CNMR1,75MHzjCDCl3i16：13861288j1284?1282|126lj779o4Z

16、11q?yellowoil；*HNMR(300MHzjCDCI3)16；?48725Im?5H,1j721-714Li1H,169D679i.mi2H)j632I,d1J=84Hzi1H)；13CNMR(75MHz?CDC1J)6：1444j1368,1322i132听128611282?1265j793<4Z13yellowoil；'HNMR(300MHziCDC1,)j6：734-119(mi5H.)1623-6,12!,mi2H)276266Imj2H)i257247Im,2H.I；1JCNMR(75MHzjCDClJ国1406,1285?1283)1262i833,359

17、)311】4El1ajyellowoil；lHNMR!,300MHzjCDCI3)16：737725I,mj5H)?711IdjJ=165Hz?1H)1677UJ=165Hzi1H)；IJCNMR(75MHziCDClJ&1373?1350?1286j1283j126Oj)064】1yellowoi：；'HNMR4El1bj237djJdjJMHziMHz?CDClJj&7=141Hzi1III17=141Hzj1H)i3CDClJi6：15918Imj2H/j70200815.197Imi2IIb6583H)；13CNMR1757j1305j127617i1364El

18、1c,1142j104oil；HNMRBrIyeHowoiK*HNMRMHzjCeniy822-817(mj2H)j746-mi2H)i3(djJ=141Hz,1H,Ij701&J7237411421HzjIHj；11CNMR(75MHziCDCIJI&2?1304j128!yellow4El1e,MHz,CDCIsh6：714134109111112ooil；1HNMRU0050-719Imj5H/j679UjIHzj1H)；11lj1336i132CNMR175MHzjCDC!3Ij6：3j1295?1294?127ll1265i4E1Hi|ye.IowMHz,CDCIJj

19、6：8'.miHzj149Br1Hb76?136MHz?CDCb!,mi1H),6Hzj1H)；1313。357243H/joil；!HIHJj7NMR30076-769713diJCNMR75MHzjCDC3)j6：3,1238j1229l1093。=1441530iIj1334Ellg?)yellowoil；'HNMRU00QvQvcu7/rjAMV?-61rkj700rjIQJ7/lllvI/03osu7j1297j1267,1242j110300MHz?CDClJi&7847yellowoil；!HNMR70Im,3HJ?763-758Imi1Hh749-737

20、tmj716UjJ=138Hzi1H):13CNMR138Hu1H)i688(diJ=MH功CDClJB137751281062l1335|13241286j5j128Oj1277j1265j1263i1268。oil；1HNMR13004Elli|yellowMHz,CDClJi6：742-724Imi5H/i68D670J尸脾帅s皿瞄母曹，吗%M珊刻嶂二册鞅蟾项翩爨州项神孤辛蓍顷m瞩骤："0Z=3：ZfiiVrfalI/*：QI3Q9S21HWN3tl1(Hl«H0SIiP)U9</H9叫i：9U£DQ9HWNH«l!。立田耳¥早圳W

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24、;PH9"HZ皿/g9u9UHI"(HEES9FI：9«/M3Q3“HJN。时HHNIH,il!»siE'|八八腥(b町"0hunt34H6”9I£仆9£*1H6U!('IH皿)技0§6(H/H8皿IMIUH徉586I-Z0I：9U"3Q。UHWMHINN0tIUHZ财96S-H93DQOoonHHN8£【6IM：9p3G3i?HINSi|HHN3E1:(HZ【£"叫”|H顷抻l2I*(HZ，叩I-H9H'HI皿)£Zi-ZE1：9*pOQO

25、，HJN。£111!)HHNhQI!。Wlh蛔Huat»9££化9£(993将H叩祯【6Hlill*0°06DM9Z【69ZI建U168ZI<831n2182EI：91P13Q3坤61*09Z1叩U*«8ZI9HIUStl3tl：H£皿严9-H第期IS,等;rP人Table1OptimiMtionoibate0®base.THFBrPh3PBr击二二124EntryBaseTimehYield%1Z:EcILDAI25666:342nBuLI27747:533L:HMDSI23170：3。4LiTM

26、P123945:555NaHMDS124459:416KHMDS124852:487KOH122461：398IBuOK122071:299Na?CO3121960:40我蹦提瑚筛选a.Reictioncondilions!imineIfl50mmol)iphosphoniumsaltiI)6(Immol)jbase(065mmol)tTHFII0mL+l0ml)；b.Isolatedr：e.d.cDeterminedbj'HNMRimlyiis.22liSiHJWiZE=342Hi6正(4%ft&：E=83：I?)i.ttflSffilIZ:E=60:40)iswill,HE

27、nlryImineRTme/hYield%、z:Ec11ab4MeC.H.127747:53to1ac4MeOC也126372:2831ad4OtNCdl.126183:1741ae2O；.NCcH<126334:665laf2i6ChC.Hj127677:2361ag2MeC.H,1274<1:9971ah2,4f6Me3C(H2126760:4081ai2naphthyl1280>99:191an1naphthyl126395:5101aaMe128463:37111a1nC«Hu126959：41121aknC16H33128153:47131amPhCH?1

28、27252:48j.Reactiontondi:ionphospbonurnfall(060mmol)jnBuLi(065mmo)iTHF110mt).78*Ci1h；:henmine(l)50mmol)THF(10mL)j78'C:ort.b.ho.liedi"Id.c.Deemby*H124NMR.anyljjii.、23施翻加选卷9JO0第册SJ-化ooO<JCJs撰上7-7-£<口一，JK%发，.，；5>I's22+!lvai-2vanp®KLJJI3wilti他婀,?Anut,J»Ift-?zrrrUni

29、65;KOJnwl-s>9<艮为，y4®=三哑应®小-nMU-XVJ-nDAEXHN-1AAJdlnTA:址-&-lr(z豕1?L-ifffl6一.siOA±S乩芳E-Rr%frffl8于龙八T-r-rL-v/r34iNwnuwluj-7/*/JL183Jrzt-abnzntnn7E«1'口八.基99>1z'产:8np彳triJE»en:亚扩着4%4utt7KM-陌:'i-nnYTSInMP4AXSMTOM9AnMBfi§IA/HH>9tz奈E-HflVIosxSNLr,h.0F

30、_ts%CJ(/A7OJ基为，-84oinfic13%-1棉'-UB-USles2mffl5项大上E9vffiT，论可83特和wftfsAF3nSvell008LuaR=2-naphthylR=2-MeCgScheme2第期W，I：倒畦施蹴顺懈泰3半靛跚立衙哑船成卤代觥的底物扩展Table3TunablestereoselecliTeolefinationofNsulfonylimineswithsemistabiliiedphosphoniumylides/_.R=2naphthylR1R?n-BuLi.THFFZ.E>99:IN，SO2RZh1+gx2R=2-MeC6H4n-

31、BuU.THFrIR2E.Z>99:14E114Z11EntryR1n!R=2naphthylR=2MeC6H,K4ZHYield'%4EHYield'%IPhBr4Z11a744E11a7724MeOC«H<Br4Z11b774E11b7434ClCf.H4Br4Z11c744E11c8144O2NC«H4Br4Z11d724E11d6952C1CJI.Br4Z11e814E11e8462pyridylBr4Z11f734Ellf7172thienylBr4Z11g704E11g7582naphthylJBr4Z11h834E11h739Ie)

32、PhCH=CHBr4ZHi764Elli74I0PhCH2CH?Br4Z11j724Ellj7011nCtHisBr4Z11k714E11k7912cyc1ohexy1Br4ZH1694EHI7213PhJCl4Z11m114E11m8414lE)PhCH=CHCl4Z11n774E11n7515PhCH2CH?Cl4Z11o694E1lo7916PhJ4Z11p724E11p7211Ie)PhCH=CHI4Z11q634E11q7618PhCLCH,I4Z11r734E11r618.Rejclionconditions：photphoniumhIHO60mmol)iX=BrForenlrie

33、t315|X=C.tndentriesml)?TSC?Ih：:henimine(050mmol)THF(10mt)j78°C:orl.b.Theilertoseletlivitywi$determm5论in->4/oopa'ir8zB)8088BRI8K0WfrKEJIffhss?,Tnft'一业1.2,i.4,56789,10Jl.AngewChemIntEd,1998?37|Jl.AngewChemIntEd,1998?37|GuoJSjDullyKJjSevensKL.TotalsynlhejisotaliohjrtinAspongijtatinI（12）

34、:187192.kenesviahydroborationoi1halo1dkynesIJ.JOrgChemi1989|54j（26）"0646067.11Conce.lonJMjBernadPLjPerezAndresJA.SamariumeictionJ.AngewChemIniEdi20fl4H3»734.1213ntEdi1999|38jrom:de$ndiodidesvEspinetPiEchivirrenAM.ThemechanismsoflheStiller（36）：47044MjauriNjSuzukiA.Palladiumca:tyzedcrosscoup

35、lingreictionsoforganoboroncompoundsJ.ChemRev,1995i95?（?）：24572483.VegiihiEiAnasiasiaL.PilladiumctiilyzedalkynylaiionJ.ChemRtvj2003i103i（5）119792017.mediatedbelleliminalioDindihalotlcobols：diastereoieIeclivesynthesisofZIvinylhalidesIj.AngewChem1116）：23842386.HodgsonDM.jArilT.Convergentandstereoselectivesyn:heji5o:trisubsliluledEa1kenriabetaoxidophosphoniumylidejJ.JAmChemSon2008i130iI49J：1650016501.Be$:mannHJiSengF.ReaclionolalkylenetriphenyIJiangLiJobGEiKlaparsA.CoppercatalyzedcouplingofapbosphoraneswithSchiflbasesJ.AngewChemIniEdi1midesandcaibamateswithvinylhalidesJ.OrgLel