Chapter 8 Reactions of Alkenes

Electrophilic Additions o Regio vs stereoselectivity Regio where do the pieces add?

Markovnikovs rule hydrogen will go to the side of the double bond with most hydrogens. Some reactions give anti-Markovnikov products Remember that if both sides of the double bond are equally substituted, then you will get a mixture of products

Stereo is there any specific stereochemical results? Anti addition the two pieces come from opposite sides of the double bond Syn addition the two pieces come from the same side of the double bond

o Addition of HX Markovnikov with rearrangement No stereoselectivity because intermediate is trigonal planar Electrons of pi bond come out to grab proton

Generates carbocation and halide ion Proton goes to less substituted side of double bond because it creates a more stable carbocation intermediate. Carbocations can rearrange!

X- attacks carbocation

ClH-Cl + H
rearrangem ent

Cl

Different halogens

HF is very slow, so you wont often see it in this reaction Rate increases as you go down the group, so HCl<HBr<HI Think about it: The first step is breaking the H-X bond, generating Xo

In terms of stability, I->Br->Cl->F-

o Addition of HBr with peroxide Anti-Markovnikov, no rearrangement No stereoselectivity because intermediate is trigonal planar Initiation The oxygen-oxygen single bond is relatively weak and can break apart to yield two radicals An oxygen radical encounters H-Br to generate an alcohol and a bromine radical
Initiation 1) 2) R RO*
O O

R Br

heat

2 RO* ROH + Br*

Propagation The bromine radical goes to the less substituted side of the double bond to generate a more stable carbon radical.

Br

Br

The carbon radical encounters H-Br and generates an alkyl halide and another bromine radical.
H * Br H Br Br + Br*

Termination Any two radicals meet

o Acid-Catalyzed Hydration of Alkenes The reverse of dehydration of alcohols Markovnikov addition of water with rearrangements possible No stereoselectivity because intermediate is trigonal planar The electrons of the pi bond grab a proton from the acid, generating a carbocation on the other side of the double bond

H+ H2O

H +

Remember that carbocations can rearrange!

H +

Water attacks the carbocation, and then deprotonates

H

H2O

+ OH

OH

What would you get if you used an alcohol as the solvent instead of water?

o Oxymercuration-Demercuration

Markovnikov addition of water without rearrangement No stereoselectivity because intermediate is free to spin around its single bond Generates an alcohol. Add Hg(OAc)2 (aq) followed by NaBH4 in subsequent step Form mercurinium ion as intermediate cant rearrange The mechanism below may make it look like you get anti addition, but there is no stereoselectivity for this reaction You wont be drawing out the mechanism of this on any test, but you need to understand it. Understanding the intermediates is essential to understanding why you get the products.

o Alkoxymercuration-Demercuration Markovnikov addition of an alcohol without rearrangement Generates an ether, not an alcohol

o Hydroboration-Oxidation

Anti-Markovnikov addition of water without rearrangement Syn addition you will get a maximum of two stereoisomers of the product BH3 acts as electrophile H2O2 and base kick boron off, leaving OH in its place Not responsible for drawing this mechanism on a test, but understanding it can help you understand why you get anti-Markovnikov, syn addition You get anti-Markovnkov because the electrons of the pi bond are coming out to grab the boron, not the hydrogen. You get syn addition because the hydrogen and boron add in one step from the same side. The boron is then oxidized off, but the OH replaces it without an intermediate.

Pretty much insignificant point You can add water to three alkenes per molecule of borane.

Catalytic Hydrogenation

Just adding hydrogen across the double bond Hydrogen is conjugated onto metal catalyst Pt, Pd, or Ni If you see Raney Nickel, just think nickel

The double bond just plops down onto the catalyst The hydrogens always add on the same side Syn addition This matters because it reduces the number of possible stereoisomers
H H H H

+
Br Br Br

Heterogeneous catalysis Term used when the catalyst is in a different phase as the reagents In this case, the catalyst is a solid

o Simmons-Smith

CH2I2 and Zn generate a carbenoid. The Zn inserts between the carbon and one iodine The carbon-zinc bond is very polar with a partial negative on the carbon If you imagine this taken to the extreme, you get a carbene.

H I C H Zn I I -

C H

+ Zn I

The carbenoid forms a three-membered ring across the double bond One step, concerted reaction Because there is no chance for the original single bond to rearrange, stereochemistry will be retained

o -elimination

Strong base turns CH2X2 or CHX3 into carbene Base abstracts proton why is this possible? o The electronegativity of the halogens makes that proton acidic enough for strong bases to abstract it. One halogen falls off

Carbene adds across double bond to form ring The ring will have 1 fewer halogen on it than the starting material. Stereochemistry is retained

Addition of halogens (X2) Need to have inert solvent

Usually a chlorinated methane (CH3Cl, CH2Cl2, or CHCl3)

Double bond attacks X2, forming halonium ion

Br

Br

Br +

inert solvent

Halide opens halonium ring

Br

Br

Br +

Br Br

inert solvent Br -

Halide goes to more substituted side, because the partial positive is stronger there.

Anti addition

o Halohydrin formation Use water instead of inert solvent First step is the same as with addition of halogens
Br H2 O Br

Br +

Double bond attacks X2, forming halonium ion

Water attacks more substituted side of halonium ring

Br +

- H+

Br

H2O

OH

The more substituted side has a greater partial positive charge

Deprotonate Anti addition

o Epoxidation

Addition of peroxy acid (RCOOOH) to alkene MCPBA is a common peroxy acid

Form a little ring with an oxygen in it Stereochemistry is retained Not responsible for drawing out this mechanism

Epoxidation with ring opening Can do this in the same reaction vessel as just the epoxidation, or can do this to an existing epoxide Protonate oxygen of epoxide Water attacks more substituted side of ring and deprotonates Anti addition

Oxidation You dont need to know these mechanisms. o Osmium tetroxide Expensive reagent Syn addition of two OHs Product is called a vicinal diol

KMnO4 (mild) What makes it mild? Another syn addition of two OHs Far less expensive, but also far less efficient

o Ozonolysis Cleaves the double bond, giving ketones and/or aldehydes Mr. Baker often gives you the products and asks for the starting material

Just put the pieces together like a puzzle!

KMnO4 (vigorous) Similar to ozonolysis, but aldehydes are further oxidized to carboxylic acids

Summary
Name Addition of HX Addition of HBr with H2O2 Acid-Catalyzed Hydration OxymercurationDemercuration Alkoxymercurati onDemercuration HydroborationOxidation Hydrogenation Simmons-Smith -elimination Additional What Reagents Adds ? HX -H, -X HBR, -H, Peroxide -Br + H2O, H -H, -OH 1)Hg(OAc -H, )2, H2O -OH 2) NaBH4 1)Hg(OAc -H, )2, ROH -OR 2) NaBH4 1)BH3 -H, 2) H2O2, -OH OH H2 and Pt, -H, Pd, or Ni -H CH2I2, -CH2ZnCu CH2X2 or CHX3 with strong base X2, inert solvent X2, H2O R-CO3H R-CO3H, H+ (aq) OsO4 KMnO4 (mild) O3 DMS (or somethin CHXor -CX2-X, -X -X, -OH -O-OH, -OH -OH, -OH -OH, -OH N/A Regioselectivit Stereoselectiv y ity Markovnikov AntiMarkovnikov Markovnikov Markovnikov Markovnikov AntiMarkovnikov N/A N/A N/A N/A N/A N/A N/A N/A Syn Syn Retention of stereochemist ry Retention of stereochemist ry Anti Anti Retention of stereochemist ry Anti Syn Syn N/A Rearrangeme nt Possible? Yes No Yes No No No No No No

Addition of halogens Halohydrin formation Epoxidation Epoxidation+ Ring Opening Osmium tetroxide KMnO4 (mild) Ozonolysis

N/A -OH to more substituted side N/A N/A N/A N/A Splits the bond and turns into a

No No No No No No N/A

KMnO4 (vig)

g else) KMnO4 (vig)

N/A

carbonyl Splits the bond and turns into a carbonyl

Further oxidizes aldehydes

To COOH