Chapter 6

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

Hydrogens on the double bond have the largest positive 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

Pt, Pd, Ni, Rh

Reaction is heterogeneous and occurs exclusively at the interface between the solid and liquid phase Catalyst is finely divided to increase surface area

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

Hydrogens add to same side of double bond

Stereochemical Implications

4 Syn-coplanar eclipsed

Unsubstituted Monosubstituted cis-disubstituted

Tetrasubstituted Trisubstituted trans-disubstituted

Highest

Lowest

Heat of Hydrogenation

Unsubstituted Monosubstituted cis-disubstituted

Tetrasubstituted Trisubstituted trans-disubstituted

Least stable

Most stable

Stability of Double Bond

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

More hindered face away from catalyst surface

Less hindered face towards catalyst surface

Steric effects can influence reactivity

Blocking the formation of the reactive intermediate What would happen if we added two methyls to the other cyclobutane apex?

Previously we saw steric effects influencing the structure and stability of molecules or intermediates
Zaitsevs Rule E vs Z isomers

The world according to Markovnikov

Occurs in variety of non-polar and polar solvents at low temperatures (-30C)

Pentane, benzene, dichloromethane, chloroform, acetic acid

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.

Hydrogen halide (acid) Alkene (base) Carbocation (conjugate acid)

Anion (conjugate base)

Electron rich -orbitals, slightly negatively charged

Positively charged end of HBr dipole

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

Proton attachs 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

Markovnikovs rule is followed: H adds to the carbon with the most Hs

Cleavage of the O-S bond at high temperature in the presence of water produces the alcohol and regenerates the sulfuric acid.

Nucleophilic attack Electrophilic attack slow

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

Water acts as Brnsted base

50% H2SO4/H20

Hydronium ion acts as electrophile

Water acts as nucleophile Hydronium ion is regenerated

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

Adding water favors formation of alcohol

Or Markovnikov does not Rule

Decomposition of peroxides ROOR

Photochemical decomposition of HBr

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

Bonds split so each moiety takes one electron

Use single barb arrows to illustrate the process

Peroxide initiator decomposes to form alkoxy radical (happens only once)

Alkoxy radical pulls H off HBr leaving Br atom

Br atom electrophilically attacks the double bond

Alkyl radical attacks HBr and removes H leading to product and Br atom

Free radicals combine to form neutral molecules

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

Lowering the Activation Barrier

Anti-Markovnikov hydration in two steps

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

Nucleophilic attack on more substituted C

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

Overall reaction Common method for formation of aldehydes and ketones

Heated in presence of oxygen or peroxides as chain initiators

Alkyl groups stabilize the carbocation intermediate