Exam 352- Exam 4

The two OH groups form the head of a man

The symmetrical bond is the bending the galaxy

Glycoside Formation (27.7A):

Forms both α-glycoside, β-glycoside

Acidic Ether Hydrolysis (27.8):

Will only hydrolyze at the anomeric carbon

Use EXCESS water

Complete Acidic Ether Hydrolysis (notes):

Etherification (27.8):

All OH groups are converted to ethers by treatment with base

Mechanism in notes

Does not form anomers

Acetalation w/ Dione (27.8):

Does not form anomers

Acytlation w/ Acid Chlorides (27.8):

Does not form anomers

NaBH₄ Reduction (27.9A)

Aldonic Acid Formation (27.9B):

DON'T use Tollens Reagent, Benedict's Reagent or Fehling's reagent

Aldaric Acid Formation (27.9B):

Oxidizes 1° alcohols and aldehydes but not 2°

Wohl Degradation (27.10):

(Shortens Aldose chain by one carbon)

[1] Oxime (aq. hydroxylamine)

[2] Cyanohydrin (acteyl group)

[3] Aldehyde (sodium methoxide)

Kiliani-Fischer Synthesis (27.10):

(Lengthens Aldose chain by one)

[1] Cyanohydrin

[2] Imine

[3] Aldehyde

N-Glycosidos Formation (27.14B):

Top: α-N-glycoside

Bottom: β-N-glycoside

α-Halo Amidification (28.2A)

Diethyl Malonate Derivative Alkylation (28.2B):

Uses diethyl acetamidemalonate

Strecker Synthesis (28.2C):

[1] α-amino nitro

[2] Cyano to carboxyl hydrolysis

Enantioselective Amino Acid Synthesis (28.4):

BINAP and rhodium moieties

Boc Protecting group (28.7):

[Boc/OtBu]

Deprotect with CF₃CO₂H, HCl, HBr

Carbamates

Fmoc Protecting group (28.7):

[Fmoc/OMe]

Deprotect with piperidine

Cbz Protecting Group (notes):

Cbz/OBn

[Boc/OtBu]:

P: (t-BuOCO)₂O, Et₃N

D: H+, H₂O

[Boc/OtBu]:

P: Isobutene, H+

D: HCl

[Cbz/OBzn]:

P: BnOCOCl, Na₂CO₃, H₂O

D: HBr or H₂/Pd

[Cbz/OBzn]:

P: PhCH₂OH, H+

D: H₂, Pd/C or OH⁻, H₂O

[Fmoc/OMe]:

P: Fmoc-Cl, Na₂CO₃, H₂O

D: Piperidine

[Fmoc/OMe]:

P: CH₃OH, H⁺

D: OH⁻, H2O

OtBu Protecting Group (notes):

Carboxyl Protecting Group (28.7):

Deprotect:

[Cbz/OBn]

CH₃COOH (hydrolysis)

H₂, Pd/C (hydrogenolysis)

Alpha-halogenation (28)

Anisole to Phenol (28)

Energy storage

Phospholipid

Phospholipid

Repellant

Biological Synthesis of Geranyl Diphosphate (29.7)

Biological Synthesis of Farnesyl Diphosphate (29.7)

Diphosphate Hydrolysis (29.7)

Isomerization (29.7):

[1] Geranyl diphosphate

[2] Linalyl Diphosphate

[3] Neryl Diphosphate

[4] Cyclization

Radical Polymerization (30.1):

[1] Initiation

[2] Propagation

[3] Termination

Disproportionation

Cationic Polymerization (30.2C):

[1] Initiation: Alkene abstracts proton from LBC

[2] Propagation

[3] Termination: Loss of a proton

Anionic Polymerization (30.2C):

Terminates with acid-base reaction

Requires a stabilizing EWG

Living polymerization (polymerization will begin again if more monomer is added)

Chiral

Meso Compound (achiral)

Random Z pattern

Lower melting point

Ziegler-Natta Polymerization (30.4):

Coordination polymerization

Forms HDPE (unbranched)

β-Elimination

Natural Rubber Synthesis (30.5):

Z-Configuration

Gutta-Percha Synthesis (30.5):

E-Configuration

Urethane (carbamate) Synthesis (30.6C):

From Isocyanate

Polycarbonate Synthesis (30.6D):

Phosgene + ROH = Lexan

Epoxy Resin Synthesis (30.6E):

Two consecutive ring openings

Add NH₂(CH₂)2NH(CH₂)2NH₂

(28.3A)