CHEMISTRY ORGANIC REVIEW

Type of addition rxn Starting Reagents Regioselective, Stereoselective? Carbocation Product

Material narkovnikov rule relocation
1Hydrohalogenation Alkene HCl, HBr, or HI Yes no Yes Adds H and cl/br/I
2Hydration Alkene H2O, H2SO4 Yes, markovnikov no Yes H and OH

Methyl? MeOH yes No Yes MeOH added

3Halogenation Alkene Br2 or Cl2 anti-addition N Br and Br

Electrophilic addition
4Halohydrin Alkene Br2 or Cl2 + Yes, markovnikov anti-addition N Br and OH
H2O,
dimethylSO3
5Oxymercuration Alkene Hg(OAc)2, H2O, Yes, markovnikov anti addition N 1. Hg-OAc+
NaBH4 2. OH replaces
HgOAc
6Hydroboration- Alkene BH3, H2O2, anti-markovnikov Yes, syn N; 1. H and BH2 syn
Oxidation NaOH addition w the OH added to addition
H and BH2, then less stable 2. OH replaces BH2
OH carbocation 3. H and OH

Type of Redox rxn reagents Staring material product

7Dihydroxylation Adds OsO4, Alkene Not Syn-addition No carbocation OH ---OH

NaHSO3, H2O regioselective relocation
8Ozonolysis O3, Me2S Alkene **the alkene is. C=O O=C
“cut” in half and
O are added
9Hydrogenation H2, Pd or Alkene no Syn addition Reduces to
Platnum, Ni alkanes (H’s syn
addition)
*Vocab:

RXN type Starting material reagents products Mechanism

To make a Alkyne from Alkane1 1. Br2 Alkyne 1. Halogenate w Br2
a alkane 2. NH2- 2. E2 w strong base
Hydrogenation Alkyne H2 Product: alkane
Addition Pd or Pt or Ni
Hydrogenation w Alkyne Pd or Pt or Ni on CaCO3 Product: alkene, cis
Lindlar’s catalyst H2
addition
Hydrogenation with Alkyne Na or Li Product: alkene trans
disssolving metal H2
NH3
Hydration Alkyne H2O , Enol –OH to ketone C-C=O Markovnikov
+ H2SO4, HgSO4 Keto-enol tautomerism

Hydroboration Alkyne For internal alkyne: BH3, Enol –OH Syn addition, anti Markovnikov
H2O2, NaOH of OH
Turns to aldehyde HC=O Tautomerism
For terminal alkyne: (resonance and stability)
sia2BH or 9BMS, H2O2, Aldehyde—Enol
NaOH
Electrophilic addition Alkyne HCl, HBr 1 equivalent= alkene Adds Br or Cl Markovnikov
for H-X 2 equivalents = alkane
(electrophilic product)
Electrophilic addition alkyne Br2, Cl2, I2 1 equivalent= alkene Two atoms of Br or Cl on each
X2 2 equivalents=alkane end of the alkyne/ alkene bond
(electrophilic product)
Stereoselectivity:
Markovnikov: the H+ will add to the carbon that has the greatest number of H already attached in that alkene bond
Anti-Markovnikov: the H+ will add to the H with less H in C-C bond
Anti-Addition: when the new electrophile is added to the intermediate it goes in on the opposite side that the halogen was added
on. (if on front then anti would be back)
Syn addition: things are added on the same side (in the red/ox additions)
Vocabs/Notes:
Oxidation: loss of electrons, add O and lose H2
Reduction: gain of electrons, lose O and gain H2

Radical RXN Starting Material Reagents Product Mechanism/notes

Substitution rxn Alkane MUST HAVE LIGHT Alkyl halide Initiation (Br homolytic cleavage) -non-stereoselectivity
Br2, Cl2, or I2 BR:BR Br. .Br both front and back
Propagation (alkane reacts w Br. attacks
yields a radical of alkane. ) -regio, Markovnikov
Termination (finishes by combines
Br. and .alkane) alkyl halide
Radical Bromination/ Alkene/ allyl Light or heat Preserved 1. NBS exposed to light or
with NBS NBS (for Br) alkene w heat and Br. Formed
NCS (for Cl) halogen on 2. Br. radically reacts w
its allyl end Alkene
3. Now w radical alkene
reacts with another Br. to
form the alkyl halide
Hydrohalogenation Alkene ROOR Alkyl halide 1. RO:OR splitsRO. .OR Br on the less stable
peroxides HBr (only works w Br) (Radical) carbon location,
Light or heat 2. RO. H—Br, radically terminal
react ROH + Br- **ANTI-Markovnikov
3. Alkene + Br-  Alkyl halide

Type Starting Carbo BEST Nu or bases Best solvent Product Stereo chemistry
 of rxn Material cations
Sn1 Substitution 2º (with poor Yes Poor Nu/weak base Protic methyls, Substitution of None/ Racemic mixture
nucleophilic 1 Nu) h2o and NU for Lv
alcohols
3º
Sn2 Substitution 1º No, Good Nu or weak base Aprotic Substitution of Inversion bc of back-side
nucleophilic 2 2º (w good concerte (pka of conj acid <11) NU for Lv attack; Ror S/
nu) d
E1 Elimination 2, 3 Yes Weak base/ good nu Protic Alkene
E2 Elimination 1,2,3 No, Strong base! Aprotic or Alkene Follows Zaitsev elimination
concerte Or bulky base like tButOK protic (alkene formed on most
*LVg and ß- d substituted C=C)
H need to be
anti in SAME **except when using bulky
PLANE, but base (t-ButO-); goes to
opposite least stable
directions
**NOTES:
*rules of LVGs and Nus are opposite
Good leaving group: stability of it as anion (anion of a strong acid) [ I-, Br-, Cl-, H2O]
Bad LVgs: OH-, F, CH3O-, NH2-
Good NU (forms bond w carbon): lone pair, has neg charge usually, linear is more stable)--
Will favor SN2; also C=C:- is good Nu small bois
Poor Nu: usually uncharged, RNH, ROH, OH2, RCOOH
Will favor SN1
Polar Protic Solvents: H2O, MeO-H, EtO-H
Favors SN1
Aprotic Polar Solvents: (no acidic protons) DMSO, DMF, acetone
Favors SN2
***E rxns will occur when the base and conjugate acid is the solvent.
Alkynes rxn Starting material Reagents Mech product
Deprotonate alkyne Alkyne Strong base (NaNH2, LDA, Base grabs proton (H) off Alkyne– that is now like a
NaH) alkyne (terminal) nucleophile
Form internal alkyne (1. )Terminal alkyne or 1. Strong base 1. Above rxn *2 equiv for internal
(2.) Nucleophilic alkyne 2. Alkyl halide (Br) 2. SN2 alkyne
Dibromide alkyne Dibromide alkane NaNH2 (2 equiv) 1. E2 (Br Leaves; strong Alkyne
base takes H)
Electrophilic Alkyne Br2 (one or two equiv) Addition w carbocations; 1. 1 equiv = alkene
addition/halogenation Br+ ion (dibromo)
2. 2 equiv =alkane
(4 bromo)
“” Alkyne HBr (1 or 2 equiv) Like from chp 6; more Adding Br and H to each
stable/substituted C side (for 2 equiv Br on
same C)
Hydration Alkyne 1. H2O Hg+ ion in the molecule Enol ketone or
2. H2SO4, HgSO4 H2O added to more stable
H+ taken by another H2O
molecule
Hydroboration Alkyne 1. (sia)2BH (for H and B(sia)2 syn add to alkyne Enol  aldehyde
terminal) The add H2O2 and NaOH, OH
2. BH3 (FOR added to less stable C
INTERNAL)
3. H2O2, NaOH
Hydrogenation alkyne H2 Alkane, reduction
Pd or Ni

“” Alkyne H2, Lindlars catalyst Alkene, CIS

Dissolve metal Alkyne Na, NH3 Alkene, TRANS

Alcohols Starting material Reagents Mech Products

Deprotonate Alcohol 2Na \/\/\O- Na+
2\/\/\OH H2
Alcoholalkyl halides Alcohol 1° or 2° HBr SN2 Alkyl halide H2O
3° SN1 for 3°
**H2O made to be leaving group on
alcohol
Alcohol  bromides 1° or 2° alcohols PBr3 SN2 Alkyl bromide where OH was
-PBr2 adds to O (substitution), inversion
*no rearrangement
*inversion @ substitution
-Br- comes in and OHPBr2 leaves
AlcoholChloride 1° or 2° alcohols SOCl2 SN2 Alkyl chloride, inverted
Et3N or pyridine -SOCl adds to O stereochemistry
-Base takes H off of OH
-OSOCL leaves when CL backside attack
Sulfonates (Make OH a good 1° or 2° alcohols MsCl or TsCl -MS adds to OH; Cl- goes off OMs on alkyl
leaving group) Et3N or pyridine -H taken off by Base This is a good leaving group
for something else
For dehydration w OMs OMs; from 1° or 2° Strong base, E2 rxn w Less stable alkene
alcohols tertbutoxide OMs leaving and alkene forming
(OtBu)
Acid catalyzed dehydration 2° or 3° alcohols H2SO4 E1 Most stable alkene
Heat Carbocation rearrangements And H2O
H donated to OH, forming OH2+ **to avoid rearragnment use
Leaving group OMs prior
Carbocat+
H2O acts as base, E1
Pinacol rearrangement Vicinal diol (two H2SO4 -One OH will form OH2 leaving group Ketone or other carbonyl
alcohol groups on C (dehydration) -Will leaving; forming carbocation (C=O) + H2O
across) -rearangment to the other OH alpha carbon
(more stability with O)
- rearrange for carbonyl
Jones 1° or 2° alcohols H2CrO4 aka Jones Carboxylic acids (from 1°
alcohols)
Ketones from 2°alcohols
PCC oxidation 1° or 2° alcohols PCC Aldehydes from 1° alcohols
Ketones from 2° alcohols
Periodic acid 1,2 Diols HIO4 “cleaves the diol”
(syn arrangement) So 2 carbonyl molecules form (
R—C=O and O=C—R)

Ethers and SM Reagents Mech Products

Epoxides
Williamsons Ether 1° or methyl alkyl halides Nu w/O- SN2 rnx w the two things Ether C—O—C
Acid catalyzed Alkene (that can form 1. Alcohols unbranched or 1° Addition to Alkene, H+ Synthesized ether
addition stable carbocations) 2. H2SO4 Then carbocation
Alcohol adds
Another C-OH takes H away
from species
Epoxide Formation Alkene MCPBA or other - Concerted Epoxide
peroxycarboxylic acid [RO=C-O- - Alkeneto O w/H Carboxylic acid
OH] - =O grabs H on O **cis and trans form different
stereochem
Halohydrins Halohydrin (with halogen Base -intramolecular substitution Epoxide and halogen anion
and OH) -Base removes H from O
*must be trans -halogen=LV
Nucleophilic Ring Epoxide 1. Nu: NaSH, NaCN, NaCCH, Nu: neg SH- or -OMe Alcohol of some kind w the Nu
opening NaOCH3 Backside attack by Nu on groups
2. H2O LESS sub Carbon *anti addition
O grabs H from H2O
Acid catalyzed ring Epoxide H2O(or other neutral Nu), 1. H3O+ donates proton to Alcohol (diol in this case with the
opening H2SO4 (other acid H+) O on epoxide H2O as nucleophile)
2. OH2 backside attack to
more substituted C
3. OH2 takes off H on the
recently added OH2