Note: the alkene is drawn in perspective.

Additions to Alkenes "Master Organic Chemistry" Note - this sheet is not meant to be comprehensive. Your course
Imagine it lying flat on a table - the H is coming masterorganicchemistry.com may provide additional material, or may not cover some of the
Reaction toward you, that's why it's drawn as a "wedge" "Regiochemistry" "Stereochemistry" reactions shown here. Your course instructor is the final authority.

H OH
R R 1) BH 3 R R Sometimes you might see BH 3THF or B 2H 6 used here: it's the same reagent in a slightly different form.
Anti-Markovnikoff syn addition
Hydroboration The base (can be NaOH, KOH, identity unimportant) helps make H 2O2 more reactive. The reaction is anti -
R H 2) NaOH, R H
Markovnikoff because the HB bond is polarized toward H (electronegativity of H = 2.2, B = 2.0) - the H
H 2O2 adds to the carbon best able to stabilize positive charge (i.e. the most substituted one).
1) Hg(OAc) 2
H 2O HO H
R R This reaction goes through 3-membered "mercurinium" ion. The NaBH 4 step removes the
Oxymercuration Markovnikoff syn + anti mercury. While the addition is anti, the overall reaction is stereorandom because this step involves a carbon
R H 2) NaBH 4 R R
R H based free radical (usually not discussed). Alternatively, an alcohol used in place of water will produce an ether.

HO H
R R H 2SO4 Strong acid protonates the alkene, generating free carbocation. Watch out for
Markovnikoff syn + anti
Acid-catalyzed addition of H 2O R possibility of rearrangements when a tertiary carbocation could be generated through a 1,2 shift.
R H H 2O R
(hydration) R H HSO 4 anion is not strongly nucleophilic, hence it does not add. Gives a mixture of syn and anti products
due to the free carbocation.
Cl H
R R HCl Markovnikoff syn + anti
Addition of HX
R H R R
R H HCl and HBr (as well as HI, not pictured) protonate the alkene to give a free
carbocation which can then be trapped by the halide anion. Gives a mixture of syn and anti
Br H
R R HBr
Addition of HX Markovnikoff syn + anti
R H R R
R H
Br
Br R R Bromonium ion mechanism
Br 2 R R R H
Bromination N/A anti addition
R H Br or H 2O/ROH depending on solvent
R R Br
The key detail in these reactions is solvent: water and alcohol solvents will form the
R H HO halohydrin products (the ones containing the OH and Br). All other solvents (you might
Br 2
Halohydrin Formation R R
Markovnikoff anti addition see CCl4, CHCl 3, hexane, etc. ) provide the dibromide.
H 2O R H
Br
Cl
R R Cl2 R R As with bromination, above. Although not depicted, use of water or alcohol as solvent
Chlorination N/A anti addition
R H R H will also lead to formation of the halohydrin product (also anti).
Cl

HO OH
R R OsO 4 R R Osmium is a transition metal. The tools won't be given in this course to fully understand how this reaction
Dihydroxylation N/A syn addition
R H works. Occasionally a second reagent like NaHSO 3, H 2S, or Na 2S2O3 is also given as a reactant in this
R H reaction - minor detail, it's used to remove the osmium from the hydroxyl groups.

HO OH Keywords are "cold, dilute". NOTE: If "heat" or "acid" is mentioned in the conditions, the diol will
R R KMnO 4 R R N/A syn addition be cleaved to provide carbonyl compounds (same reaction as ozonolysis with oxidative workup,
Dihydroxylation R H cold, dilute R H below).

O
OH O
R O O RCO 3H is a peroxyacid. A common peroxy acid for this reaction is m-CPBA
R R R R N/A syn addition Cl OH
Epoxidation (m-chloroperoxybenzoic acid). If H 3O+, heat is written afterwards, this
R H R H O
is opening of the epoxide to give the diol (anti-selective) m-CPBA

H2 H H
R R R R N/A syn addition The catalyst can vary - you might see Pt or Ni as well. All provide the same product with the same
Hydrogenation
R H Pd/C R H stereochemistry.

H Br
R R HBr Peroxides generate the Br radical, which adds to the double bond in the way that will generate the
Radical addition of HBr Anti-Markovnikoff syn + anti most stable radical (i.e. the radical will go on to the most substituted carbon). This explains the
R H peroxides R R
R H selectivity for the anti-Markovnikoff product. It gives a mixture of syn and anti because it goes through
(RO-OR) a free radical process.
O3
Ozonolysis (Reductive workup) R R
O + O
S R H Reductive workup: Zinc (Zn), or dimethyl sulfide (DMS, Me 2S) is a reducing agent. It reduces excess ozone, allowing for isolation
R R CH3 CH3 (or Zn/H+)
of the aldehyde.
R H
O3 R R Oxidative workup: Hydrogen peroxide is used to obtain the carboxylic acid instead of the aldehyde.
O + O Can also use KMnO 4 and acid
Ozonolysis (Oxidative Workup) R OH
H 2O2 Omissions, Mistakes, Suggestions?
This reaction goes through addition of a carbene (actually, "carbenoid") to james@masterorganicchemistry.com
H H
CH2I 2 C the double bond. The reaction is stereospecific.
R R R R This sheet copyright 2015, James A. Ashenhurst
Cyclopropanation N/A syn addition Another set of conditions to provide a cyclopropane is CHCl3 with strong
R H masterorganicchemistry.com
Zn/Cu R H base (NaOH), which makes the dichlorocyclopropane.