Alkene/Alkyne RXN + Sn1/Sn2/E1/E2

H-X (Br, Cl, I)

adds one Br, Cl, I, markovnikov, can rearrange

H₂SO₄ or H₃O⁺

adds H and OH, markovnikov, can rearrange

H-Br, ROOR

adds one Br, anti-markovnikov

1. Hg(OAc₂), H₂O

2. NaBH₄

adds H and OH, markovnikov, no rearrangements bc no carbocation

1. BH₃-THF

2. H₂O₂, NaOH

adds H and OH, anti-markovnikov, no rearrangements

H₂SO₄ or H⁺, CH₃OH

add H and OR, markovnikov, can rearrange

1. Hg(OAc)₂,CH₃OH

2. NaBH₄

adds H and OR, markovnikov, can’t rearrange

H², Pd/C or Pt/C or Ni/C

adds two H’s, syn addition, turns alkenes/alkynes to alkanes

Br₂/CCl₄ or CHCl₂

adds two halogens, anti addition

X₂/H₂O or ROH

adds halogen and OH or OR, markovnikov (but halogen is on less substituted), anti addition

RCO₃H (aka MCPBA)

epoxidation (triangle), syn addition

1. MCPBA (RCO₃H)

2. H₃O⁺

adds two OH’s, anti addition

1. OsO₄

2. NaHSO₃ or Na₂SO₃

or

KMnO₄ (cold, diluted)/NaOH

adds two OH’s, syn addition

1. O₃

2. (CH₃)₂S (aka DMS) or Zn,H₂O

splits and reduces to a ketone and aldehyde

1. O₃

2. H₂O₂

or

1. KMnO₄ (hot, concentrated)

2. H₃O⁺

splits and reduces to a ketone and carboxylic acid

acid catalyzed hydration of alkynes

tautomerization of enol and keto

hydroboration-oxidation of alkynes

tautomerization of enol and keto (aldehyde)

ozonolysis of internal alkyne

2 carboxylic acidsoz

onolysis of terminal alkyne

carboxylic acid and CO2

NaNH₂

forms new bonds

lindlar’s catalyst (Pd/BaSO₄/quinoline)

reduce to cis alkene

Na/NH₃

reduces to trans alkene

weak nucleophile/weak base

ROH, RCOOH, H₂O

strong nucleophile/weak base

CN^-, N₃^-,Cl^-, Br^-, I^-, RS,^- HS^-, RSH, H₂S, RNH₂, R₃P

strong nucleophile/strong base

OH^-, RO^-

bulky bases

t-buO, DBN, DBU, LDA

aprotic solvents

acetone, DMF, DMSO, acetonitrile

3 - weak nuc/weak base

E1 (high temp) or SN1 (low temp)

3 - strong nuc/weak base

SN1

2 - strong nuc/weak base

SN2

1 - strong nuc/weak base

SN2

3 - strong nuc/strong base

E2

2- strong nuc/strong base

E2

1 - strong nuc/strong base

SN2

bulky bases are___

always E2

large, broad trough far to the left (3000-3600)

OH group

medium-sized peak at ~2200 cm^-1

nitrile (C≡N)

big, pointy peak at 1700 ± 50 cm^-1

carbonyl (C=O)

reduce aldehydes, acid chlorides, and acid anhydrides to primary alcohols

LiAlH₄ and NaBH₄

reduce ketones to secondary alcohols

LiAlH₄ and NaBH₄

reduce esters and carboxylic acids to primary alcohols

LiAlH₄

KMnO₄ or H₂CrO₄ or CrO₃/H₂SO₄ (Jones reagent)

makes carboxylic acid from primary alcohol

1. Mg (Grignard reagent - replaces halogen with Mg)

2. CO₂

3. H₃O⁺

makes carboxylic acid from alkyl halide

amide

ester

acid anhydride

acid halide

increasing reactivity of carboxylic acid derivatives

amide - ester - acid anhydride - acid halide

ROH + strong acid

converts carboxylic acid to an ester (fischer esterification)

1. NaOH

2. H₃O⁺

converts ester to carboxylic acid (saponification)

reduce esters and acid chlorides to primary alcohols

LiAlH₄

reduce amides to amines

LiAlH₄

1. DIBAL-H, -70C

2. H₂O

reduces ester to aldehyde

1. LTBA

reduces acid chloride to aldehyde

Br₂/NaOH

reacts with primary amide to give primary amine

1. LiAlH₄

2. H₂O

nitrile to primary amine

1. H₃O⁺

2. heat

nitrile to carboxylic acid