1/19
kms
Name | Mastery | Learn | Test | Matching | Spaced |
---|
No study sessions yet.
Oxidation of Alcohols
reagents: PCC, CH2Cl2
primary alc. → aldehyde
secondary alc. → ketone
COOH → ketone
Grignard: 1. 2 eq. RMgX, 2. H3O+
Organolithium: 1. 2 eq. R—Li, 2. H3O+
1st eq. acts as a base, 2nd eq. acts as a nuc.
nitriles (CN) → ketone
Grignard/R—Li (1 eq.)
H3O+
acid chloride → ketone
R2—CuLi (1 eq.) (dialkyl lithium cuprate)
esters + nitriles → aldehydes
DIBAL-H
H2O
acid chloride → aldehyde
LiAlH(tBuO)3 (bulky LiAlH)
H2O
aldehyde → primary alc., ketone → secondary alc.
NaBH4, H2O
ALL carbonyls → alcohols
LiAlH4/LAH, H2O (“removes” carbonyl)
COOH → ester
ROH , H+ (acid catalyst): Fischer esterification
Hydration Rxns (H—O)
base conditions: OH-, H2O → nuc attack, proton transfer
acid conditions: H3O+, H2O → proton transfer, nuc attack
only formaldehyde is favored in equilibrium
Acetal Formation (R—O)
base: R—O-, ROH
acid: R-OH2+, ROH
hemiacetal intermed: RO and OH group
Cyclic Acetal Formation
diol (HO—CH2—CH2—OH), H3O+
useful protecting group (reactivity: acid chlorides (induction) > aldehydes > ketones > esters)
Imine Formation (C=N—R)
R-NH2, H+
Enamine Formation (C=C—N—R2)
R2—NH, H+
Oxime Formation (C=N—OH)
HO—NH2, H+
Hydrazone Formation (C=N—NH2) + Reduction
formation: HO—NH2, H+
reduction: NaOH/KOH, H2O, heat → reduces to alkane
Cyanohydrin Formation (OH + CN)
HCN
OR 1. NaCN, 2. H2O/HCN
Reducing Nitriles (CN)
CN → C—NH2: 1. LiAlH4, 2. H2O
CN → COOH: H3O+
Wittig Rxn
preparing reagant: SN2, 1. PPh3, 2. BuLi (any strong base like NaH)
rxn: R=PPh3
alternative: HWE reagent → (RO)2(O=P)=C—COOR
favors (E) stereochem if Ph group is stabilized/conjugated (Z if not)
Baeyer-Villiger Oxidation (ketone → ester, aldehyde → COOH)
RCO3H (MCPBA)
embedded O in ester adds to more sub. C
O for aldehyde adds to H