UCLA 14D RXN Reagents

Hydride Reduction of Aldehydes and Ketones

NaBH4, MeOH

//

1.LiALH4,Et2O

2. H2O

Preparation of Organometallic Reagents

Alkyl halide, Mg0/Li0, Et2O

Organometallic Reduction of Aldehydes and Ketones

1. RMgX, Et2O // 1. RLi, Et2O

2. H2O

PCC oxidation of alcohols

PCC, CH2CL2

Jones Oxidation of alcohols

CrO3, H2SO4, acetone, H2O

(primary alcohol to carboxylic acid)

Reduction of Ketones and Aldehydes to Alkanes

Zn(Hg), HCl

(EWG to EDG if on arene)

Oxidation of Alkanes to Ketones and Aldehydes

CrO3, H2SO4, H2O

(EDG to EWG if on arene)

Guaranteed Deprotonation of Alcohols

NaH/NaNH2, DMF

Tosylation

TsCl, Pyridine

Forced E1 on Alcohol

TsOH, ∆

Bromine Substitution of an Alcohol

PBr3

(only works on primary or secondary, because is SN2)

Chlorine Substitution of an Alcohol

SOCl2, Et3N

(only works on primary or secondary, because is SN2)

Williamson Ether Synthesis from Alcohol

1. NaH, DMF

2. RX, DMF

Industrial Synthesis of Ethers

H2SO4, ∆

Basic epoxide opening

1. Base (including organometallic or hydride), Et2O

2. H2O

Acidic Epoxide Opening

H2SO, Protic Solvent that doubles as Nuc // HX only

Diels-Alder Reaction

Diene, Dienophile, ∆

Hydrohalogenation of Alkene

HX

(Markovnikov, full racemic)

Dihalogenation of Alkenes

X2, CCl4

(anti racemic)

Halohydrin Formation from Alkene

X2, H2O

(OH to more subst. Carbon, anti racemic)

Acid Catalyzed Hydration of Alkenes

H2SO4, H2O

(Markovnikov, full racemic)

Oxymercuration-Reduction of Alkenes (Hydration RXN)

1. Hg(OAc)2, H2O 2. NaBH4, NaOH, H2O

(Markovnikov, full racemic)

Hydroboration-Oxidation of Alkenes (Hydration RXN)

1. BH3, THF

2. H2O2, NaOH, H2O

(NON-Markovnikov, syn racemic)

Epoxidation of Alkenes

MCPBA, CH2Cl2

(syn racemic)

Catalytic Hydrogenation of Alkenes

H2, Pd/C, EtOH

(syn racemic (maintains cis/trans relationships of other substituents in 3D))

Dihydroxilation of Alkenes

1. OsO4, THF

2. H2S

(syn racemic)

Ozonolysis of alkenes

1. O3, CH2Cl2

2. DMS

Deprotonation of Terminal Alkyne

NaNH2, Et2O

Hydrohalogenation of Alkynes

HX

(Markovnikov, full racemic (whether cis/trans or R/S) if in excess, RXN continues until alkyne is saturated to alkane)

Complete Hydrogenation of Alkynes

H2, Pd/C, EtOH

Lindlar's Partial Hydrogenation of Alkynes

H2, Lindlar's Catalyst, EtOH

(makes cis alkenes)

Birch's Partial Hydrogenation of Alkynes

1. Na0, NH3

2. H2O

(makes trans alkenes)

Acid And Mercury Catalyzed Hydration of Alkynes

HgSO4, H2O, H2SO4

(Markovnikov Carbon gets 2 H, other alkyne C gets double bond O after tautomerization (e.g. Ketone from terminal Alkyne))

Hydroboration-Oxidation of Alkynes

1. Dicyclohexylborane (Cy2BH), THF

2. H2O2, NaOH, H2O

(Markovnikov Carbon gets double bond O, other alkyne C gets 2 H after tautomerization (e.g. Aldehyde from terminal Alkyne))

halogenation of Arenes

X2, FeX3

(EWG substituent, but uniquely still para/ortho directing)

Addition of SO3H (Sulfonation) to Arenes

SO3, H2SO4

(EWG substituent)

Addition of NO2 (Nitration) to Arenes

HNO3, H3SO4

(EWG substituent)

Friedel-Crafts Alkylation of Arenes

RCl, AlCl3

(NB: mechanism changes for primary vs. tertiary RCl)

(EDG Substituent)

Friedel-Crafts Acylation

Cl-Carbonyl, AlCl3

(EWG Substituent)

Reduction of Nitroarenes (NO2 to NH2)

Zn(Hg), HCl

(EWG to EDG)

Oxidation of Aryl Amines (NH2 to NO2)

F3C2HO3 (trifluoroperacetic acid)

(EDG to EWG)

Base Catalyzed Geminal Diol Formation from Ket/Al (Addition of H2O)

NaOH, H2O

(not synthetically useful except with formaldehyde)

Acid Catalyzed Geminal Diol Formation from Ket/Al (Addition of H2O)

H2SO4, H2O

(not synthetically useful except with formaldehyde)

Acetal Formation from Ket/Al (Addition of ROH)

H2SO4, Alcohol

(OHROH can be used to form cyclic acetals)

Imine Formation from Ket/Al (Addition of Amines)

H2SO4, Primary Amine/Ammonia

Amine Formation from Imine

NaBH3CN, MeOH

Alpha Alkylation of ket/al

1. LDA, THF

2. RX

Alpha halogenation of ket/al

X2, AcOH

Aldol Formation

NaOH, H2O

(Unlike geminal diol formation, OH acts as base rather than nucleophile)

crossed aldol reaction

NaOH, H2O

(involves 2 different carbonyls as reagents. Not Selective: any of four products are possible)

aldol condensation

NaOH, H2O, ∆

(forms the aldol reaction product, then the heat allows OH to be protonated and kicked out by a double bond)

Preparation of COOH with CO2

1. CO2, Et2O

2. H2O

Fischer Esterification of COOH

ROH, H2SO4, ∆

Amide Formation from COOH

Ammonia/Amine, ∆

Reduction of COOH to Primary Alcohol

1. LiAlH4, Et2O

2. H2O

Acyl Chloride Formation from COOH

SOCl2, CH2Cl2

Hydrolysis of Acyl Chloride

H2O

Alcoholysis of Acyl Chloride

ROH

Aminolysis of Acyl Chloride

Amine

Acid Catalyzed Hydrolysis of Esters

H2SO4, H2O, ∆

Base Catalyzed Hydrolysis of Esters (Saponification)

NaOH, H2O, ∆

Transesterification

H2SO4, ROH, ∆

Aminolysis of Esters

Amine

Reduction of Acyl Chloride/Ester/Amide

1. LiAlH4, Et2O

2. H2O

Addition of Organometallic Reagent to Carbonyl Derivatives

RMg, Et2O