Orgo 1 Mechanisms

alkene

HX

alkyl halide

X=Cl/Br; markov addition

yes rearrange

alkene

X2

1,2-Dihalide

anti addition (trans)

alkene

H2O / H+

alcohol

markov addition

yes rearrange

alkene

X2 / H2O

halohydrin

-OH on more subs carbon (markov)

trans

alkene

1) Hg(OAc)2, H2O

2) NaBH4

alcohol

markov

alkene

1) BH3

2)H2O, NaOH

alcohol

antimark

syn addition of OH and H

alkene

1) O3

2) CH3SCH3

aldehydes/ketones

cleaves C-C bond, adds O to ends

alkene

1)OsO4

2) NaHSO3

1,2-diol

syn addition (cis)

alkene

H2/ Pd

alkane

syn addition

alkyne

HX

alkyl halide

x=Cl,Br markov

alkyne

excess HX

alkyl 1,1- dihalide

x=Cl,Br markov

alkyne

X2

1,2-dihalide

anti addition (trans)

alkyne

excess X2

1,1,2,2-tetrahalide

alkyne-terminal

H2O/H2SO4/HgSO4

ketone

markov

mix of two products

alkyne-terminal

1)BH3

2) H2O2, NaOH

ketones and aldehydes

anti mark addition

alkyne

H2/Lindlar

z-alkene

syn addition

alkyne

H2/Pd

alkane

2 additions

alkyne

Li/NH3

E-alkene

anti addition

alkyne terminal

NaNH2

alkynyl anion

deprotonation of terminal alkyne

alkyl halide (Me, 1 prime, 2 prime)

alkynyl anion

elongated alkyne

substitution of halide for alkynyl nucleophile

SN2

NaNH2 to deprotonate alkyne

alkane

Cl2/ light

alkyl chloride

not regioselective

(cl can go anywhere)

alkane

Br2 / light

alkyl bromide

Br goes to more substituted spot

3 prime> 2 prime> 1 prime

alkene

NBS/ light

allylic bromide

replacement of H on carbon adjacent to double bond

alkene-terminal

HBr / peroxides

alkyl bromide

anti- mark (less substituted)

alkyl halide (Me, 1 prime, 2 prime)

lewis base/ good nuc

substitution product

SN2-- inversion***

(frequent: -CN, N3-, X-, carboxylate anion)

alkyl halide (3 prime, allylic, benzyllic)

Lewis base/ good nuc

substitution products

SN1- can be racemic***

can rearrange

alkyl halide (3 prime, allylic, benzylic)

weak base/ weak nuc/ STRONG acid

alkene

E1 Zaitsev

can rearrange

common: H2SO4

alkyl halide (1 prime, 2 prime, 3 prime)

KOtBu

alkene

E2- anti coplanar

(strong bulky base for primary)

(for secondary or tertiary: -OH, deprotonated alkyne, -OR, -NR2)

alchohol

alkali metal (Li or Na or K)

alkoxide

alcohol

NaH

alkoxide

alcohol

H2SO4

alkene

zaitsev; E1 or E2

alcohol

HX

alkyl halide

racemization

can rearrange

alcohol

PBr2

alkyl bromide

inversion

alcohol

SOCL2/ pyridine

alkyl chloride

inversion

alcohol

TsCl/ pyridine

tosylate

retention

alcohol

MsCk/ pyridine

mesylate

retention

tosylate

lewis base

substitution product

SN2

Mesylate

Lewis Base

substitution product

SN2

1 prime alcohol

swern or

dess martin or

PCC

aldehyde

1 prime alcohol

H2CrO4

carboxylic acid

2 prime alcohol

any ox reagent

ketone

1,2- diol

HIO4

dialdehyde

breaks C-C bond

alkyl halide

NaSH

thiol

SN2

thiol

oxidant

disulfide

disulfide

reductant

thiol

ether

HX

alkyl halide + OH

alcohol can react again, SN1 or SN2

can rearrange if SN1

alcohol

R3SiCl / Et3N

silly ether

alcohol protecting group

silly ether

BuNF

alcohol

deprotonation

alkene

peracids

epoxide

syn addition

halohydrin

NaOH

epoxide

allylic alcohol

sharpless

1,2- epoxide 3-ol

enantioselective

epoxide

lewis base

epoxide opening

less hindered C

epoxide

1)LiAlH4

2) H2O

alcohol

hydride adds to less hindered C

alkyl halide (Me, 1 prime, 2 prime)

alkoxide

ether

SN2

alkene

alcohol/ H+

ether

markov

alkyl halide

Na2S

sulfide

SN2 twice

sulfide

H2O2

sulfone

sulfone

NaIO4

sulfoxide