ACS: Reactions + Reagents

H2, Pd/Pt/Ni

Alkene or alkyne → fully hydrogenated alkane

H2, Lindlar catalyst

Alkyne → cis alkene

Na, NH3

Alkyne → trans alkene

HX with alkene

Markovnikov alkyl halide

HBr, ROOR with alkene

Anti-Markovnikov alkyl bromide

H2SO4, H2O with alkene

Markovnikov alcohol; rearrangements possible

Hg(OAc)2, H2O; NaBH4

Alkene → Markovnikov alcohol; no rearrangement

BH3·THF; H2O2, OH−

Alkene → anti-Markovnikov alcohol; syn addition

Br2 or Cl2 with alkene

Anti addition to vicinal dihalide

Br2, H2O

Alkene → halohydrin; OH to more substituted carbon

mCPBA

Alkene → epoxide

OsO4

Alkene → cis-1,2-diol

Cold KMnO4

Alkene → cis-1,2-diol

Hot KMnO4

Alkene oxidative cleavage to ketones/acids

O3, Zn or DMS

Alkene ozonolysis to aldehydes/ketones

O3, H2O2

Alkene ozonolysis to carboxylic acids/ketones

HX 1 equivalent with alkyne

Vinyl halide

HX 2 equivalents with alkyne

Geminal dihalide

HBr, ROOR with alkyne

Anti-Markovnikov vinyl bromide

HgSO4, H2SO4, H2O

Alkyne hydration → ketone

BH3; H2O2, OH− with terminal alkyne

Terminal alkyne → aldehyde

Br2/Cl2 excess with alkyne

Tetrahalide

NaNH2 with terminal alkyne

Forms acetylide ion

NaNH2 then R-X

Terminal alkyne alkylation; extends carbon chain

Cl2 or Br2, hv

Alkane radical halogenation

NBS, hv

Allylic or benzylic bromination

NaOH with alkyl halide

SN2 alcohol or E2 alkene depending substrate

RO− with alkyl halide

Strong nucleophile/base; SN2 or E2

t-BuOK

Bulky base gives Hofmann alkene by E2

NH3 with alkyl halide

Alkyl halide → amine

NaCN with alkyl halide

Alkyl halide → nitrile

NaN3 with alkyl halide

Alkyl halide → azide; can reduce to amine

ROH with alkyl halide

Weak nucleophile; SN1 ether formation possible

Ag2O, H2O

Alkyl halide → alcohol

PBr3

Alcohol → alkyl bromide

SOCl2

Alcohol → alkyl chloride

TsCl or MsCl

Alcohol → tosylate/mesylate leaving group

H2SO4, heat with alcohol

Alcohol dehydration → alkene by E1

POCl3, pyridine

Alcohol → alkene by E2; no rearrangement

PCC

Primary alcohol → aldehyde

PCC with secondary alcohol

Secondary alcohol → ketone

CrO3/H2SO4

Primary alcohol → carboxylic acid

CrO3/H2SO4 with secondary alcohol

Secondary alcohol → ketone

Br2, FeBr3

Benzene bromination

Cl2, FeCl3

Benzene chlorination

HNO3, H2SO4

Benzene nitration

SO3, H2SO4

Benzene sulfonation

RCl, AlCl3

Friedel-Crafts alkylation

RCOCl, AlCl3

Friedel-Crafts acylation

KMnO4 hot with alkylbenzene

Alkylbenzene → benzoic acid

Sn/HCl

Nitro group → amine

H2/Pd

Nitro group → amine

NaNO2, HCl

Aromatic amine → diazonium salt

CuCl

Diazonium → aryl chloride

CuBr

Diazonium → aryl bromide

CuCN

Diazonium → aryl nitrile

H3PO2

Diazonium → H

H2O, heat with diazonium

Diazonium → phenol

NaBH4

Aldehyde/ketone → alcohol

LiAlH4

Strong reduction of carbonyls, acids, esters, amides, nitriles

DIBAL-H

Ester or nitrile → aldehyde

RMgX

Grignard reagent; adds carbon group to carbonyl

RLi

Organolithium; adds carbon group to carbonyl

RMgX + CO2

Grignard → carboxylic acid after acidic workup

HCN

Aldehyde/ketone → cyanohydrin

ROH, H+

Carbonyl → acetal

H3O+

Acetal → carbonyl

Primary amine

Carbonyl → imine

Secondary amine

Carbonyl → enamine

NH2OH

Carbonyl → oxime

NH2NH2

Carbonyl → hydrazone

NH2NH2, KOH, heat

Wolff-Kishner reduction; carbonyl → alkane

Zn(Hg), HCl

Clemmensen reduction; carbonyl → alkane

Ph3P=CHR

Wittig reagent; carbonyl → alkene

SOCl2 with carboxylic acid

Acid → acid chloride

PCl3 or PCl5

Acid → acid chloride

ROH with acid chloride

Acid chloride → ester

NH3/amine with acid chloride

Acid chloride → amide

H2O with acid derivative

Acid derivative → carboxylic acid

LiAlH4 with ester

Ester → primary alcohols

LiAlH4 with amide

Amide → amine

LiAlH4 with nitrile

Nitrile → amine

LDA

Carbonyl → enolate

NaOH with aldehyde/ketone

Aldol reaction

NaOH, heat after aldol

α,β-unsaturated carbonyl

NaOR with ester

Claisen condensation

Malonic ester synthesis

NaOEt, R-X, H3O+/heat → substituted carboxylic acid

Acetoacetic ester synthesis

NaOEt, R-X, H3O+/heat → methyl ketone

H3O+ with nitrile

Nitrile → carboxylic acid

Gilman reagent R2CuLi

Conjugate addition to α,β-unsaturated carbonyl

Grignard with enone

Usually 1,2-addition

Weak nucleophile with enone

Usually 1,4-conjugate addition

Enolate + enone

Michael addition

Michael addition then aldol

Robinson annulation

KMnO4 vs O3

Both cleave alkenes; workup determines aldehyde vs acid outcomes

PCC vs Jones

PCC stops primary alcohol at aldehyde; Jones oxidizes to acid

Hydroboration vs oxymercuration

Hydroboration gives anti-Markovnikov OH; oxymercuration gives Markovnikov OH

Lindlar vs Na/NH3

Lindlar gives cis alkene; Na/NH3 gives trans alkene

Friedel-Crafts alkylation vs acylation

Alkylation rearranges; acylation does not

SNAr vs benzyne

SNAr needs ortho/para EWG; benzyne needs very strong base/heat