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1、飪讓糍2O1OChineseJournalofCatalysisV_01.3lNo.9文章編號:0253.9837(2010)09—1098.05國際版DOI:101016/S1872-2067(10)60106—4研究論文:1098~1102基于甲磺?;幕酋0罚贝甲鳛榇呋┑牟粚ΨQ炔基化反應新配體金薇,黃永波,萬伯順中國科學院大連化學物理研究所,遼寧大連I16023摘要:以商業(yè)易得的(一)一麻黃堿、(+)一偽麻黃堿和各種手性氨醇為主要原料,經(jīng)過簡單的兩步反應,合成了一系列基于甲磺?;幕酋0芬话贝?SAA)配體,并將其用于催化苯乙
2、炔基鋅對醛的不塒稱加成反應.在沒有Ti(OiPr)等金屬試劑的條件下,配體表現(xiàn)出較好的不對稱誘導能力,取得了高達83%ee.關鍵詞:磺酰胺一氨醇配體;不對稱加成;炔基化反應;醛中圖分類號:0643文獻標識碼:AMethylsulfonyl--BasedSulfamide--AmineAlcoholasaLigandforEnantioselectiveAlkynylationofAldehydesJINWei,HUANGYongbo,WANBoshunDalianInstituteofChemicalP}{vsics,ChineseAc
3、ademyofSciences,Dalian116023,Liaoning,ChinaAbstract:Chiralmethylsulfonyl—basedsulfamide—aminealcohol(SAA)ligandsweresynthesizedfromcommerciallyavailablestartingma—terialsintwosimplesteps.Methylsulfonyl—basedSAAligandscatalyzedtheasymmetricalkynylationofvariousaldehydesus
4、ingalkynylzinctoprovidechiralpropargylalcoholswithmoderatetogoodenantioselectivityupto83%ee.Keywords:sulfamide—aminealcohol;enantioselectiveaddition;alkynylation;aldehydeThecatalyticenantiOselectiveadditionofterminala1methanesulfonylrTObasedSAAwerealsoeffectiveforthekyne
5、stoaldehydesisaveryusefulmethodforthesynthesisasymmetricalkynylationofcarbonylcompounds[36-38].ofchiralpropargylalcohols,whichareimportantversatileInordertounderstandtheelectronicandstericeffectsofbuildingblocksofmanybiologicallyactivecompoundsandchiralSAAonasymmetricalk
6、ynylationofaldehydesandasnaturalproducts[1_4].Inrecentyears,chiralligands,suchpartofextendingtheapplicationofourSAAligands,weasN—methylephedrine[5,6],sulfonamidealcohol[7,8],reportmethylsulfonyl(Ms)一basedSAAcatalyzedenanti—BIN0Landitsderivativesf9—121,havesuccessfullybee
7、noselectivealkynylationofaldehydesunderverymildcondi—usedinthisreaction.However,Ti(O-'Pr)4orothermetaltionswithoutusingmoisturesensitiveTi(O-'Pr)4andspeciesareusuallynecessaryinmostofthesecatalyticsys—Zn(OTf1,.terns[13~17].Ontheotherhand[18—32],efficientligandsthatcanbep
8、reparedfromcheapandeasilyavailablestarting1Experimentamaterialsinafewsyntheticstepsandthataredesignedfo