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Alkene Addition Reactions
Alkene Addition Reactions
The planarity of the sp2 hybridized carbons and their substituents exposes the -bond to attack from above or below the plane The higher electronegativity of the sp2 hybridized carbons makes them have a slight negative charge
Syn hydrogenation
Breaking a H-H bond and the C-C bond Making 2 C-H bonds Bonds in the product are stronger Reaction is exothermic H is negative Heat of hydrogenation is the amount of heat evolved so it has a positive sign Without a catalyst the activation barrier is high so that uncatalyzed hydrogenation is very slow
Rapid at room temperature Usually in high yield and only one product Solvent chosen based on reactant solubility
Hydrogen is absorbed on the surface of the catalysts Strong H -bond is broken and two weak H-metal bonds are formed Alkene is absorbed on the surface bond is broken and two weak C-metal -bonds are formed An H atom diffuses on the surface until it encounters the alkene and the weak metal atom H and C bonds are replaced by a strong C-H -bond A second H diffuses until it encounters the free radical and the weak metal atom H and C bonds are replaced by a strong CH -bond The alkene desorbs and the catalysis site is ready for adsorption of another alkene
Stereochemical Implications
4 Syn-coplanar eclipsed
Highest
Lowest
Heat of Hydrogenation
Least stable
Most stable
Alkane product is formed in the syn configuration with alkene substitutients in eclipsed positions In 1,2 substituted cycloalkenes, the addition exclusively forms the cis-isomer In alkenes with bulky substitutents (eg bridged-cyclalkanes) steric effects force the less hindered face of the double bond against the metal surface, so that is the face the hydrogens will add to.
Bridged ring structure on cyclohexene makes an extremely rigid structure Methyl groups on cyclobutane ring overhang the double bond restricting access
Previously we saw steric effects influencing the structure and stability of molecules or intermediates
Zaitsevs Rule E vs Z isomers
The weaker the hydrogen halide bond (the more acidic the hydrogen) the faster the reaction rate
HF << HCl < HBr < HI
Hydrogen halide (electrophile) acts as an acid and protonates the -bond of the alkene forming a carbocation in the rate limiting step.
Alkyl groups are electron releasing The more alkyl groups on the double bond, the more electron rich the -bond becomes The more electron rich, the more attractive to electrophilic attack, increasing reactivity The positive charge develops on the carbon that bears the most electron releasing alkyl groups
Halide ion acts as nucleophile and attacks the electrophilic carbocation forming alkyl halide in a fast step
In an unsymmetrically substituted alkene, the hydrogen adds to the carbon with the greatest number of hydrogens, and the halogen adds to the carbon with the fewest number of hydrogens Protonation of the double bond leads to a carbocation, so regioselectivity comes from the stability of the carbocation with more stable one favored Final product has slightly higher energy since there are steric effects of the alkyl with the halide substitutent
More stable 2 carbocation forms here
Exothermic reactions Primary transition state has much higher activation energy than secondary transition state. So transition state with secondary carbocation characterisitics is more likely to form and is immediately captured by the nucleophilic attack by the anion Secondary and primary halide possible products differ little in energy
Carbocation intermediates can undergo hydride shifts to lead to the more stable tertiary carbocation Presence of products due to rearrangment supports argument that carbocations are reaction intermediates
Sulfuric acid (strong acid conditions) can also add to alkenes by a similar mechanism of protonation followed by addition of the hydrogen sulfate anion to the most stable carbocation intermediate
More stable secondary carbocation is formed and Hydrogen sulfate anion adds hydration heat
1.
Hydronium ion acts as the electrophile protonating the double bond leading to more stable carbocation
Rate-determining step Markovnikov Rule is followed The more stable the carbocation, the faster the reaction rate
2. 3.
Water acts as nucleophile adding to form alkyloxonium ion Water acts as Bronsted base to deprotonate the alkyloxonium ion and forming the alcohol regenerating the hydronium ion
50% H2SO4/H20
Acid catalyzed hydration is the reverse of acid catalyzed dehydration of alcohols Principle of Microscopic Reversibility applies Le Chateliers Principle applies
A system at equilibrium adjusts so as to minimize a stress applied to it
Intentional addition of peroxides Unintentional formation of alkylperoxides when oxygen is not excluded O-O bond is weak yielding two alkoxy radicals Alkoxy radical attacks the HBr, pulling off H to form the alcohol, leaving neutral Br atom
Alkyl radical attacks HBr and removes H leading to product and Br atom
More stable alkyl radical sets regioselectivity Opposite to Markovnikovs rule since Br adds first in the less stable position
Secondary alkyl radicals more stable than primary alkyl radicals so H adds to the C with the most substitution
HBr is only hydrogen halide that reacts by either electrophilic or free radical addition HI and HCl always add by electrophilic mechanism The Big Idea Use HBr to under varying conditions to choose whether the product follows Markovnikov Rule or goes opposite to Markovnikovs Rule
Borane dimerizes readily and then stabilized by the ether, often THF
Four center transition state has carbocation character, so positive charge is favored on most substituted carbon, leading to regioselectivity
Empty p orbital Addition is syn
NO chance for rearrangements in transition state Steric effects favor boron on less substitute C Repeats for each H on the boron
Nucleophilic attack of hyperperoxide anion on boron Alkyl group migrates from boron to oxygen during hydroxide elimination with preservation of stereo chemistry Water in electrophilic attack forms another 4 center transition state yielding the alcohol
Works with Cl2 or Br2 at room temperature in variety of organic solvents No rearrangements so either carbocations are not intermediates OR nucleophilic capture is faster than rearrangement Anti addition is observed Formation of 3-center bromonium ion intermediate
Bromonium ion intermediate
Br is polarizable
The more substituted the alkene, the faster the reaction rate
Consistent with rate determining step being electron flow from alkene to the halogen Alkyl electron releasing groups stabilize the transition state for bromonium ion formation
Bridging of the bromine in the bromonium ion forces the bromine anion into attack on the opposite face of the double bond leading to trans addition in cycloalkenes
Halogen addition in water adds X and OH 1st step is formation of halonium bridged ion 2nd step is nucleophilic attack by water
Electrophilic attack
Deprotonation
Follows Markovnikov Rule in that nucleophile adds to more substituted carbon Addition is in cycloalkenes will be anti because bridged halonium ion prevents syn approach
Overall transformation : C=C to epoxide Reagent : a peracid or peroxyacid, RCO3H Regioselectivity : not relevant since both new bonds are the same, C-O Stereoselectivity : syn since the two new C-O bonds form at the same time from the peracid. The reaction is an example of a concerted process (all bonding changes occur in one step) Since the reaction is concerted the stereochemistry of the alkene is preserved in the product.
For example if the alkyl groups of the alkene are cisthen they are also cis- in the epoxide.
Start at the C=C as the nucleophile, make a bond to the slightly electrophilic O break the weak O-O make a new C=O break the original C=O to make a new O-H bond, break the original O-H to form the new C-O bond ! (phew !) bond to give the epoxide.
Most common reagent is peroxyacetic acid Solvents are acetic acid , dichloromethane or chloroform Substitutions increase rate of reaction since alkyl groups release electrons to the double bond
Implies peroxyacid acts as an electrophilic reagent towards the double bond