Facilitator: Chris Lovero Organic Chemistry Reactions 1 Task Reaction NotesH HH CH3HBrAddition of HX(Mark)*Adds a halide to more substituted carbon.H HH CH3HBrROORAddition of HX(Anti-Mark)*Adds a halide to least substituted carbon.Br2CH2Cl2(or CCl4)Add two Br's antito alkene*Anti and co planarCH3DAdding a Br andOH (Mark w/ Br as Hand anti-planar)CH3DBr2H2OForming alkenefrom vicinal dihalide*Anti and co planarBrBrCH3CH3HHNaI or KIacetone*Wedges with wedges and dashes with dashes*E2 Like!Dehydration toalkene OH*E1 like and it cannot give terminal alkeneH2SO4heatOHPOCl3heat*SPECIAL REACTION: dehydrates to form terminal alkene.Addition of OH(direct and mark)CH3CH3*CANNOT CONTROL STEREOCHEM!*Low yield!*C+ formation!H3O+Facilitator: Chris Lovero Organic Chemistry Reactions 2 Task Reaction NotesOxymercuration/demercuration(Add OH from alkenemark and antiplanar)*Complex mechanism*Mark and antiplanarCH3D1) Hg(OAc)2/ H2O2) NaBH4Hydroboration(Add Oh anti-mark andsyn planar)*Anti-mark*Notice PeroxideCH3D1) BH3 / THF2) H2O2 / -OHSPECIAL: Adds alcoholinstead to form ethers!CH3D1) Hg(OAc)2/ CH3OH2) NaBH4*Complex mechanism*Mark and antiplanar*WILL BE SEEING THISMORE IN ORGO IICH3CH3DCH3 H2 Pt, Pd, or NiCatalytic Hydrogenation(Alkenes -> Alkane, SynAddition of H)*Steric factors must bepayed attention to*Can use D2 insteadFormation ofVicinal Diols(Syn)CH3DCH3DOsO4H2O2KMnO4cold, basic*expensive*toxic*great yield*cheaper*safer*poor yieldFacilitator: Chris Lovero Organic Chemistry Reactions 3 Task Reaction NotesOzonolysis(double bond cleavage)*Can use Zn/acetic acid instead of (CH3)2S*Can isolate the formaldehyde.1) O3 / CH2Cl22) (CH3)2SRR RR+1) O3 / CH2Cl22) (CH3)2SHR RR+1) O3 / CH2Cl22) (CH3)2SHR HR+Warm KMnO4 cleavageKMnO4warmRR RR+HR RR+HR HR+KMnO4warmKMnO4warm+*further oxidizes to form carboxylic acids*cannot isolate the formaldehydeCarbene / Carbenoidaddition (formation ofcyclopropane)CH3DCH2N2heatDH CH3CH3CH2I2Zn(Cu)*syn*stereochem is preserved*Second reaction uses the Simmons-Smith reagentFormation of epoxidesfrom alkenes*useful for synthesis (ESPECIALLY IN ORGO II)CH3DMCPBAFacilitator: Chris Lovero Organic Chemistry Reactions 4 Task Reaction NotesOpening of EpoxidesNOTE: Can use RO- to form ethers. Youwill see this in Orgo II.*acidic conditions opens from more substituted side.*Basic are like SN2 (least substituted side)*Please look up mechanism.H3O+H2OCH3DOCH3DO1)-OH2)H3O+Formation ofDibromocarbenes andDichlorocarbenesCH3DDH CH3CH3CHCl3KOHCHBr3KOHFormation of theacetylide anionCH3C C HNaNH2*forms the nucleophile that is handy when connecting carbons!Uses of the acetylideanionwith methyl or 1o halidesCH3C C-CH3Br*SN2 because of the exception we learned from before!!!!with 2o or 3o halidesCH3C C-CH3CHCH3Br*E2 remember from last test!!!with carbonyl groups (ketones, aldehydes, and formaldehydes)CH3CCH3OCH3C C-1)2) then H3O+*acetylide anion attacks partially positive carbon*DO NOT FORGET then H3O+*please look up the mechanism so you can see how the carbene is formedFacilitator: Chris Lovero Organic Chemistry Reactions 5 Task Reaction NotesSynthesis of Alkynes*Need either geminal or vicinal dihalides*Look up mechanism*NaNH2 gives terminal*KOH gives internal1) NaNH2 / 100oC2) H3O+CH3CHCH CH3BrBrCH2CHCH2CH3BrBrCH3CCH2CH3BrBrCHCH2CH2BrBrCH3KOH200oCHalogenation of alkynesBr2 and alkyneCH3C C HBr2(1 eq)+*Stereochem cannot be controlledHBr and alkyneCH3C C HHBr(1 eq)HBr(2 eq)*Mark*syn additionHBr and alkyneCH3C C HHBrROOR*Anti mark*syn additionCatalytic reduction withreactive catalystCH3C C CH3 H2 Pt, Pd, or Ni*Takes it all the way back to alkane*generally bad yieldFacilitator: Chris Lovero Organic Chemistry Reactions 6 Task Reaction NotesAlkyne to Alkene:TRIPLE to DOUBLE*isolates an alkene witha SYN addition of HH2 / Pd(BaSO4)quinolineCH3C C CH3Lindlar's catalystDissolving metalCH3C C CH3 NaNH3*isolates an alkene withan ANTI addition of HAddition of H-OH toalkynesMercuric IonCH2C C HCH3HgSO4 / H2OH2SO4HgSO4 / H2OH2SO4CH2C C CH3CH3+*Mark addition*If not terminal, you will get a mixture.*Formation of ketoneHydroborationCH2C C HCH31) Sia2BH2) H2O2 / -OH*Antimark addition*will get a mixture if not terminal*Formation of aldehydeOxidation of alkynes(mild conditions)CH3C C CH3KMnO4 / H2Oneutral / coldCH3C C HKMnO4 / H2Oneutral / cold*Forms vicinal carbonyls*further oxidizes terminal alkynes to form carboxylic acid.Facilitator: Chris Lovero Organic Chemistry Reactions 7 Task Reaction NotesCleavage of Alkynes:*Forms H2O and CO2if terminal.CH3C COxidation of alkyne (strong)1) KMnO4 / H2O2) -OH / heatCH3C C H1) KMnO4 / H2O2) -OH / heat++CDH2+Ozonolysis1) O3 2) H2OCH3C CCDH2+CH3C C H++1) O3 2) H2O*Same products as previousThe Grignard ReagentCH CCH3BrH Mg ether*Forms from 1o, 2o, 3o, allyl, vinyl, and aryl carbons.The OrganolithiumReagentCH2BrCH3 Lipentane or hexane*This reagent acts like grignard but is stronger.Formation of alcoholsfrom Grignard1o alcohols. (Grignard and formaldehyde)MgBrOHH1)2) H3O+*Know this mechanism!*Carbon attachment2o alcohols. (Grignard and aldehyde)MgBrOH1)2) H3O+*Know this mechanism!*Carbon attachment3o alcohols. (Grignard and ketone)MgBrO*Know this mechanism!*Carbon attachment1)2) H3O+Facilitator: Chris Lovero Organic Chemistry Reactions 8 Task Reaction NotesGrignard and estersor acid halides*Reaction goes until completion*Know this mechanism!MgBrOOCH31)2) H3O+Grignard and Epoxides(opening of epoxides)O1)2) H3O+MgBr*SN2 like (attacks least substituted side)*Know this mechanism!Attaching Deuterium tocarbonsCH3MgBrD2O*This is just good to know.Corey-House ReactionCH3BrLiCuI+*not well understood (do not need to know mechanism)*another way to attach carbons.Hydride reduction ofcarbonylsmild conditions (NaBH4 as reagent)ONaBH4EtOHOClNaBH4EtOH*reduces only aldehydes and ketones.*use alcohols as a solvent.strong conditions (LiAlH4 as reagent)OOH1) LiAlH4 / ether2) H3O+OO1) LiAlH4 / ether2) H3O++*reduces aldehydes, ketones, esters, acid