Reagents sem 1 Flashcards by evan kang

What is the function of Br2, hv

Puts Br in the most stable radical spot
- reacts via free radical mechanism
- mostly used for synthesis of 3° alkyl bromides

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What is the function of NBS, hv or ROOR

puts Br at the most stable radical position, avoiding the C=C

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Describe a reaction on an alkane-OH with acids:
1) conj base is nuc
2) Conj base is not nuc

1) HCl, and HBr
- Sn1 mechanism adds nuc to C+
2) H2SO4, and H3PO4
- E1 mechanism makes C=C

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Describe a reaction of (acids) being added to an alkene?

1) Adds H+X Markovnikov addition
2) C+ intermediate (rearr)
- ends racemic
- ex. HCl, HBr, HI

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Describe a reaction of (acids + peroxide) being added to an alkene?

1) Adds H+X Anti-markovnikov
2) radical mechanism

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Alkene + (H2SO4, H2O)

1) Adds H+OH mark
2) C+ int (Rearr)
- ends racemic

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Alkene + [ 1)Hg(OAC)2, ROH 2)NaBH4 ]

1) Adds H+OH Mark
2) anti addition
3) Hg mercurnium int
- no rearr
- ends racemic

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Alkene + [ 1)BH3, THF 2)H2O2, NaOH ]

1) Adds H+OH anti-Mark
2) syn addition
- no rearr
- ends racemic

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Alkene + [ X2, inert solvent ]

1) adds X+X anti addition
2) Halonium intermediate
3) racemic
X2 = Cl2, Br2, I2
inert = CH2Cl2, CHCl3, CCl4

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Alkene + [ X2, H2O ]
- can also be ROH

1) Adds X+OH anti-addition
2) halonium int
3) OH attacks more substituted
4) racemic
- can also result in OR addition

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Alkene + [ H2, Pd ]

1) adds H+H syn addition
2) does not react with C=O or Ar-ring
3) racemic
- Other catalysts include Pt or Ni

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Alkene + [ CH2N2 + Δ or hv ]
or
Alkene + [ CH2I2 + ZnCu or CuCl2 ]

1) adds CH2 to alkene forming 3 membered ring
2) Syn addition
3) racemic

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Alkene + [ CHCl3 + KOH ]

1) adds 3 membered ring with 2 X attatched
2) Syn add
- works with CHBr3

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Alkene + [ mCPBA + inert ]

1) adds epoxide syn-addition
2) peroxyacid (anything with 3 O’s)
- see card 9 for inert

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Alkene + [ mCPBA + H3O+ ]

1) adds OH+OH anti add
2) epoxide int

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Alkene + [ 1)OsO4 2)H2O2 ]

1) adds OH+OH syn add

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Alkene + [ 1)KMnO4 2) KOH ]
- cold

1) adds OH+OH syn add

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Alkene + [ KMnO4, H3O+ ]

1) breaks alkene and adds =O to both C’s
2) ends with CA and Ket
- oxidative cleavage

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Alkene + [ 1)O3 2)(CH3)2S ]

1) breaks alkene and adds =O to both C’s
2) ends with ket and ald

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terminal Alkyne + [ NaNH2 ]

1) deprotonated alkyne
2a) SN2 on methyl or 1° alkyl halides
2b) E2 on 2° or 3° alkyl halides
3) can be used “like” grignards on C=O

dihalide or halide + [KOH, EtOH] or [NaNH2, Δ]

elimination to form alkene if halide or alkyne if dihalide

Alkyne + [H2, lindlars catalyst]
- also [H2, Ni2B]

1) H+H syn add
2) ends in alkene

Alkyne + [Na, NH3]

1) H+H anti add
2) ends in alkene

Describe a reaction of [acids] being added to an alkyne?

1) adds H+X mark
2) depends on # mol
- if enough alkyne –> alkane

Describe a reaction of [**X2, inert**] being added to an alkyne?

1) adds X+X anti 2) depends on # mol - if enough alkyne --> alkane

Describe a reaction of [**acids + ROOR**] being added to an alkyne?

1) adds H+X anti-mark 2) depends on # mol - if enough alkyne --> alkane 3) ONLY WORKS WITH HBr

Alkyne + [**H2O, H2SO4, HgSO4**]

1) adds H+OH Mark 2) anti-add

Alkyne + [**1)Sia2BH 2) H2O2, NaOH**]

1) adds H+OH anti-mark 2) syn-add

Alkyne + [**KMnO4, H2O**]

1) adds =O to both C's of alkyne 2) ends in ketones or CA - final product is alkane version of reactant + carbonyls

Alkyne + [**1)KMnO4, KOH, H2O, Δ 2) H3O+**]

1) breaks alkyne and adds =O to both C's 2) ends in ket and CA

Alkyne + [**1)O3 2)H2O**]

1) breaks alkyne and adds C=O to both C's 2) Terminal H is untouched

ROH + [**Na or K]

1) deprotonates OH creates alkoxide (RO-) 2) NaOH can be used on phenol

What happens when an acid chloride or ester reacts with 1) grignard reagent 2) H3O+

1) 2eq or organometal (R-MgBr or R-Li) added 2) Mild NH4Cl or H2O used if results in 3° alcohol - alkyl halide + mg, ether = R-MgBr - strong base so epoxide opens less hindered carbon

What happens when Sp3 or Sp2 halide react with gilman reagents? - R2CuLi

1) Adds R like Sn2 reaction in place of LG

Carbonyl + [**1)LiAlH4 2)H3O+**]

1) reduces carbonyl to alcohol - reduces all carbonyls

Carbonyl + [**1)NaBH4 2)CH3OH**]

1) reduces carbonyl to alcohol - reduces only aldehydes and ketones

benzaldehyde + [**H2, Raney Ni**]

1) gets rid of all double bonds 2) end in 1-cyclohexylmethanol

ROH + [**strong oxidation agent**]

1) Turns OH into ketone or CA - strong reagents look for Cr, acid

ROH + [**mild oxidation agent**]

1) Turns OH into ketone or aldehyde

ROH +[**NaOCl, Tempo**] - what happens if it is in excess?

1) turns OH into ketone or aldehyde - if excess then it can end in CA

ROH +[**TsCl, pyridine**] - or MsCl, pyridine

1) turns OH into OTs or OMs - these are good leaving groups

ROH + [**SOCl2**] - or (COCl)2

1) converts OH into Cl - retains stereochemistry

ROH + [**PBr3**] - or PI3

1) converts OH into Br or I - inversion of stereochemistry

glycol+ [**HIO4**]

1) cleaves glycol 2) ends with aldehydes and ketones - only works on cis geminal alcohols

CA + ROH + acid

1) fischer esterification - forms ester via PAD PAD mechanism

Acid chloride + ROH + base

1) forms ester via basic mechanism - better than fischer cuz acid chloride is more reactive

Ether + [**Strong acid (HBr or HI)**]

1) cleaves ester 2) adds halide on both cleaved part - 1° and 2° alkyl halides via Sn2 rxn - 3° alkyl halides via Sn1 - exception, phenol keeps OH cuz 2° sp2 SN2 rxn not possible

ROH with TIPSCl and TBAF

1) TIPSCl protects OH turning it into TIPSO 2) TBAF removes protection