Chemistry Synthesis Practice

Alkyl Halide —— lengthened simple alkane

Gilman Reagent

Alkene/Alkyne —— Alkane

1. H2 2. Pd, Pt, or Ni

Grignard/organolithium on alkane —— alkane

Water

Alcohol —— Tosylate Ester

1. TsCl, pyridine

Tosylate Ester —— Alkane alkyl halide

Halogen, room temperature (Sn1 for tertiary or secondary)

Alkene —— Alkyl halide (markov, rearrangements)

HBr

alkene —— alkane alkyl halide

HBr/ROOR (anti-mark)

primary or secondary alcohol —— alkane alkyl halide

PBr3, PCl3, I2 (Sn2)

Alkene —— alkene alkyl halide

Br2/NBS

Alcohol —— alkane alkyl halide

HBr

Primary or secondary alcohol —— alkyl chloride

SOCl2 (stereochemistry retention)

Alcohol —— alkyl chloride

ZnCl2 (Sn1 for 2 and 3, Sn2 for 1)

alkyne —— geminal dihalide

HBr/ROOR (anti-mark)

Alkene —— vicinal dihalide

Br2/CCl4

alkyne —— vicinal tetrahalide

Br2/Cl2 CCl4

alkyne —— geminal dihalidea

HBr/HCl/HI

alkene —— halohydrin (alcohol with halogen)

Br2, Cl2/H2O

alkene —— vicinal glycol/diol

KMnO4 H2O cold or OsO4, H2O2 (syn)

epoxide —— vicinal glycol/diol or alcohol + other functional group

1. H3O+ and CH3OH or -OCH3

alkene —— alcohol

1. BH3, THF 2. H2O, H2O2 (anti-markov)

alkene —— alcohol (markov, anti)

1. Hg(OAc)2 2. NaBH4

Alkene —— alcohol

H3O + /H2O (rearrangements, weak nuc)

formaldehyde —— lengthened primary alcohol

1. Grignard 2. ether/H3O+

aldehyde —— lengthened secondary alcohol

1. Grignard 2. ether/H3O+

ketone —— lengthened tertiary alcohol

1. Grignard 2. ether/H3O+

ketone/aldehyde —— alcohol

1. NaBH4 acid or 1. LiAlH4 acid

esters/carboxylic acid —— alcohol

1. LiAlH4, acid

carbonyl —— alcohol

Raney Ni H2

epoxide —— lengthened alcohol

1. grignard ether H3O+ oh on more subbed carbon,

Glycol —— carbonyl

HIO4

alkene —— ketones/aldehydes

1. O3 2. (CH3)2S

secondary alcohol —— ketone

PCC, CCl4; Na2Cr2O7

primary alcohol —— aldehyde

PCC, CCl4, NaOCl, Tempo, DMSO (COCl2)

internal alkyne —— diketone

KMnO4, H2O

enol —— ketone

base / acid

terminal alkyne —— aldehyde

1. Sia2BH 2. H2O2, NaOH anti-markovnikov

alkene —— ketones, carboxylic acids

1. KMnO4, H3O+ (Hot)

terminal alkyne —— diketo-acid

KMnO4, H2O

alkyne —— ketones and carboxylic acids

KMnO4, basic hot or 1. O3 H2O

primary alcohol —- carboxylic acid

Na2Cr2O7; excess NaOCl, Tempo

alkyne —— trans alkene

1. Na 2. NH3

alkyne —— cis alkene

1. H2 2. Lindlars CatalystA

alcohol —— alkene

1. H2SO4, H3PO4

alkane —— alkene

E1 — weak base; E2 strong base

tosylate ester —— alkene

OtBU, heat favors E reaction

acetylide —— two alkenes

secondary or tertiary alkyl halide

alkene alkyl halide —— internal alkyne

KOH (fused)

alkene alkyl halide —— terminaal alkyne

NaNH2, acid

acetylide —— lengthened alkyne

primary alkyl halide

alkyne —— secondary alcohol with alkyne addition

1. NaNH2 2. PhCHO 3. H2O2

ketone —— tertiary alcohol with alkyne addition

1. acetylide 2. H3O+

alkyne — enol

1. HgSO4 2. H2SO4 H2O

alkyne —— acetylide

1. NaNH2

vicinal glycol —— ketone and all other subsitutents

1. H2SO4, heat

R — X —— R — Mg — X

1. Mg Ether

R- X —— R-Li

2 Li

alcohol —— alkoxide

NaHo

phenyl —— phenoxide

NaOH

alcohol —— ether (Williamson)

1. NaH (alkoxide) 2. primary alkyl halide or tosylate

acid chloride / Ester —— tertiary alcohol

1. Grignard 2. Ether, H3O+

Cu —— gilman

2 lithium alkanes

alkyl halide —— thiol

NaSH

2 thiols —— lengthened alkane with S-S

Br2

Thiol —— sulfionic acid

HNO3, KMnO4

acid chloride —— tosylate ester

1. tscl pyridine

alcohol —— ester

1. carboxylic acid 2. H2SO4

alkene —— epoxide

MCPBA

tosylate ester —— alkane

LiAlH4