Chapter 8
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Chapter 8. Alkenes and Alkynes II: Addition Reactions. Addition Reactions of Alkenes. p -bond. s -bond. 2 s -bonds. 1A.How To Understand Additions to Alkenes. This is an addition reaction: E – Nu added across the double bond. Bonds broken. Bonds formed.

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Chapter 8

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Chapter 8

Chapter 8

Alkenes and Alkynes II:

Addition Reactions


Chapter 8

Addition Reactions of Alkenes


1a how to understand additions to alkenes

p-bond

s-bond

2 s-bonds

1A.How To Understand Additions to Alkenes

  • This is an addition reaction: E–Nu added across the double bond.

Bonds broken

Bonds formed


Chapter 8

  • Since p bonds are formed from the overlapping of p orbitals, p electron clouds are above and below the plane of the double bond.

p electron clouds


Chapter 8

  • Electrophilic

    • electron seeking

    • C=C and C≡C p bonds are particularly susceptible to electrophilic reagents (electrophiles)

  • Common electrophile

    • H+, X+ (X = Cl, Br, I), Hg2+, etc.


Chapter 8

  • In an electrophilic addition, the p electrons seek an electrophile, breaking the p bond, forming a s bond and leaving a positive charge on the vacant p orbital on the adjacent carbon. Addition of B– to form a s bond provides an addition product.


Chapter 8

Electrophilic Addition ofHydrogen Halides to Alkenes: Mechanism and Markovnikov’sRule

  • Mechanism:


Chapter 8

  • Mechanism

    • Sometimes do not go through a “free carbocation”, may go via:


Chapter 8

  • Markovnikov’s Rule

    • For symmetrical substrates, there is no regiochemistry problem.


Chapter 8

  • Markovnikov’s Rule

    • But for unsymmetrical substrates, two regioisomers are possible.


Chapter 8

  • Markovnikov’s Rule

    • In the electrophilic addition of an unsymmetrical electrophile across a double bond of an alkene, the more highly substituted and more stabilized carbocation is formed as the intermediate in preference to the less highly substituted and less stable one.


Chapter 8

  • Markovnikov’s Rule

    • Thus:

Note: carbocation stability  3o > 2o > 1o


Chapter 8

  • Addition of Hydrogen Halides

    • Addition of HCl, HBr and HI across a C=C bond.

    • H+ is the electrophile.


Chapter 8

  • Energy profile:


2a theoretical explanation of markovnikov s rule

2A.Theoretical Explanation ofMarkovnikov’s Rule

  • One way to state Markovnikov’s rule is to say that in the addition of HX to an alkene, the hydrogen atom adds to the carbon atom of the double bond that already has the greater number of hydrogen atoms.


Chapter 8

Step 1

Step 2


Chapter 8

  • Energy profile:


Chapter 8

  • Examples


2b modern statement of markovnikov s rule

2B.Modern Statement of Markovnikov’s Rule

  • In the ionic addition of an unsymmetrical reagent to an unsymmetrical double bond, the positive portion of the added reagent attaches itself to a carbon atom of the double bond so as to yield the more stable carbocation as an intermediate.


Chapter 8

  • Examples


Chapter 8

  • Examples


2c regioselective reactions

2C.Regioselective Reactions

  • When a reaction that can potentially yield two or more constitutional isomers actually produces only one (or a predominance of one), the reaction is regioselective.


2d an exception to markovnikov s rule

2D.An Exception to Markovnikov’s Rule

  • Only with HBr in presence of peroxide.

  • Via a radical mechanism (see Chapter 10).

  • This anti-Markovnikov addition does not take place with HI, HCl, and HF, even when peroxides are present.


Chapter 8

Stereochemistry of the IonicAddition to an Alkene

attack from top

racemate

achiral

trigonal planar

carbocation

attack from bottom


Chapter 8

4. Addition of Sulfuric Acid to Alkenes

more stable

3o cation

less stable

1o cation

  • Addition of H–OSO3H across a C=C bond.


4a alcohols from alkyl hydrogen sulfates

4A.Alcohols from Alkyl HydrogenSulfates

  • The overall result of the addition of sulfuric acid to an alkene followed by hydrolysis is the Markovnikov addition of H– and –OH.


Chapter 8

Addition of Water to Alkenes:Acid-Catalyzed Hydration

  • Overall process:

    • Addition of H–OH across a C=C bond.

    • H+ is the electrophile.

    • Follow Markovnikov’s rule.


Chapter 8

5A.Mechanism


5b rearrangements

5B.Rearrangements

  • Rearrangement can occur with certain carbocations.


Chapter 8

Alcohols from Alkenes throughOxymercuration–Demercuration:Follows Markovnikov Addition.

  • Step 1: Oxymercuration

  • Step 2: Demercuration


6a regioselectivity of oxymercura tion demercuration

6A.Regioselectivity of Oxymercura-tion–Demercuration

  • Oxymercuration–demercuration is also highly regioselective and follows Markovnikov’s rule.


6b rearrangements rarely occur in oxymercuration demercuration

6B.Rearrangements Rarely Occur inOxymercuration–Demercuration

  • Recall: acid-catalyzed hydration of some alkenes leads to rearrangement products.


Chapter 8

See slide 30 also.


Chapter 8

  • Rearrangements of the carbon skeleton rarely occur in oxymercuration–demercuration.

no rearrangement


6c mechanism of oxymercuration

6C.Mechanism of Oxymercuration

There is no “free carbocation”.


Chapter 8

  • Stereochemistry

    • Usually anti-addition.


Chapter 8

  • Although attack by water on the bridged mercurinium ion leads to anti addition of the hydroxyl and mercury groups, the reaction that replaces mercury with hydrogen (step 2) is not stereocontrolled. This step scrambles the overall stereochemistry.

  • The net result of oxymercuration–demercuration is a mixture of syn and anti addition of –H and –OH to the alkene.


Chapter 8

  • Solvomercuration-Demercuration

Note:

Step 1 with THF-HOH gives an alcohol.

Step 1 with THF-ROH gives an ether.


Chapter 8

Alcohols from Alkenes throughHydroboration–Oxidation:Anti-Markovnikov Syn Hydration

  • BH3 is called borane.

  • Addition of H–BH2 across a C=C bond.


Chapter 8

  • BH3 exists as dimer B2H6 or complex with coordinative solvent.


Chapter 8

  • An anti-markovnikov product results:

syn addition

Anti-Markovnikov addition

of “H” & “OH”


Chapter 8

  • Compare with oxymercuration-demercuration:

anti addition

Markovnikov addition

of “H” & “OH”


Chapter 8

Hydroboration: Synthesis ofAlkylboranes


8a mechanism of hydroboration

8A.Mechanism of Hydroboration


Chapter 8

  • Other examples


8b stereochemistry of hydroboration

8B.Stereochemistry of Hydroboration

  • Syn addition


Chapter 8

Oxidation and Hydrolysis ofAlkylboranes

B always ends

up on the least

hindered carbon


Chapter 8

  • Oxidation


Chapter 8

  • Via


Chapter 8

  • Hydrolysis


Chapter 8

  • Overall synthetic process of hydroboration-oxidation-hydrolysis.

  • Overall: anti-Markovnikov addition of H–OH across a C=C bond.

  • Forms regioisomer opposite to oxymercuration-demercuration.


Chapter 8

anti-Markovnikov

syn addition

  • Example

This oxidation step occurs with retention of configuration


Chapter 8

Summary of Alkene HydrationMethods


Chapter 8

  • Examples

With rearrangement

Markovnikov addition of H2O, no rearrangement

anti-Markovnikov, syn addition of H2O

No rearrangement


Chapter 8

Protonolysis of Alkylboranes

  • Protonolysis of an alkylborane takes place with retention of configuration; hydrogen replaces boron where it stands in the alkylborane.

  • Overall stereochemistry of hydroboration–protonolysis: syn.


Chapter 8

  • e.g.


Chapter 8

Electrophilic Addition of Bromine and Chlorine to Alkenes

  • Addition of X–X (X = Cl, Br) across a C=C bond.


Chapter 8

  • Examples


12a mechanism of halogen addition

12A. Mechanism of Halogen Addition

Br–Br bond becomes polarized when close to alkene.

(vincinal

Dibromide)

(cyclic bromonium ion)


Chapter 8

  • Stereochemistry

    • Anti addition


Chapter 8

Stereospecific Reactions

  • A reaction is stereospecific when a particular stereoisomeric form of the starting material reacts by a mechanism that gives a specific stereoisomeric form of the product.


Chapter 8

  • Reaction 1

  • Reaction 2


Chapter 8

  • Addition of bromine to cis-2-Butene

(a)

(b)


Chapter 8

  • Addition of bromine to trans-2-Butene

(a)

(b)


Chapter 8

Halohydrin Formation

  • Addition of –OH and –X (X = Cl, Br) across a C=C bond.

  • X+ is the electrophile.

  • Follow Markovnikov’s rule.


Chapter 8

  • Mechanism


Chapter 8

  • Other variation

    • If H2O is replaced by ROH, RÖH will be the nucleophile.


Chapter 8

Divalent Carbon Compounds:Carbenes

15A. Structure and Reactions ofMethylene


Chapter 8

(Resonance forms)


Chapter 8

15B. Reactions of Other Carbenes:Dihalocarbenes

  • :CX2 (e.g. :CCl2 = dichlorocarbene).

  • Generation by a-elimination of chloroform.

  • Note: E1 & E2 are β-eliminations.


Chapter 8

  • :CCl2 usually gives a syn (cis) addition across a C=C bond.


Chapter 8

  • Stereospecific reactions


Chapter 8

15C. Carbenoids: The Simmons-SmithCyclopropane Synthesis

  • I-CH2-ZnI is the Simmons-Smith reagent.


Chapter 8

  • I-CH2-ZnI gives a stereospecific syn (cis) addition across a C=C bond.


Chapter 8

Oxidation of Alkenes:Syn 1,2-Dihydroxylation

  • Overall: addition of 2 OH groups across a C=C bond giving a vicinal diol.

  • Reagents:dilute KMnO4 / OH⊖ / H2O / cold or OsO4, pyridine then NaHSO3, H2O.


Chapter 8

16A. Mechanism for SynDihydroxylation of Alkenes


Chapter 8

  • Both reagents give syn dihydroxylation.


Chapter 8

  • Comparison of the two reagents

    • KMnO4: usually lower yield and possibly side products due to over-oxidation.

(oxidative cleavage of C=C)

  • OsO4: usually much higher yield but OsO4 is extremely toxic.


Chapter 8

Oxidative Cleavage of Alkenes

17A. Cleavage with Hot BasicPotassium Permanganate


Chapter 8

  • Other examples


Chapter 8

17B. Cleavage with Ozone


Chapter 8

  • Examples


Chapter 8

  • Mechanism


Chapter 8

Electrophilic Addition of Bromine & Chlorine to Alkynes


Chapter 8

Addition of Hydrogen Halidesto Alkynes

  • Regioselectivity

    • Follow Markovnikov’s rule.


Chapter 8

  • Mechanism


Chapter 8

  • As with akenes, Anti-Markovnikov addition of hydrogen bromide to alkynes occurs when peroxides are present in the reaction mixture.


Chapter 8

Oxidative Cleavage of Alkynes

OR

  • Example


Chapter 8

How to Plan a Synthesis:Some Approaches & Examples

  • In planning a synthesis we often have to consider four interrelated aspects:

    • Construction of the carbon skeleton.

    • Functional group interconversions.

    • Control of regiochemistry.

    • Control of stereochemistry.


Chapter 8

21A. Retrosynthetic Analysis

  • How to synthesize ?

  • Retrosynthetic analysis


Chapter 8

Markovnikov addition

of H2O

  • Synthesis


Chapter 8

  • How to synthesize ?

  • Retrosynthetic analysis

  • Synthesis

anti-Markovnikov addition of H2O


Chapter 8

21B. Disconnections, Synthons, andSynthetic Equivalents

  • One approach to retrosynthetic analysis is to consider a retrosynthetic step as a “disconnection” of one of the bonds.

  • In general, we call the fragments of a hypothetical retrosynthetic disconnection Synthons.


Chapter 8

  • Example

  • Retrosynthetic analysis

(gem-dibromide came from addition of HBr across a C≡C bond.)


Chapter 8

  • Retrosynthetic analysis

synthons

disconnection

synthetic equivalent


Chapter 8

  • Synthesis


Chapter 8

21C. Stereochemical Considerations


Chapter 8

  • Retrosynthetic analysis

    • The precursor of a vicinal dibromide is usually an alkene.

    • Bromination of alkenes are anti addition.

(rotate 180o)

(anti addition of Br2)

(anti addition of H2)


Chapter 8

  • Synthesis

(anti addition of H2)

(anti addition of Br2)


Chapter 8

 END OF CHAPTER 8 


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