organic - clutch ch. 10 - addition...

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CH. 10 - ADDITION REACTIONS

CONCEPT: GENERAL MECHANISM

□ Addition reactions are ones in which 1 ______ bond is broken and 2 new ______ bonds are formed.

● They are the inverse of ___________________ reactions

EXAMPLE: Provide the mechanism for the following addition reaction.

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CONCEPT: MARKOVNIKOV’S RULE

□ When we try to perform addition on asymmetric double bonds, we now get two possible products.

● Markovnikov’s Rule predicts that the carbocation will ALWAYS form on the _________ _______________ carbon


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CONCEPT: HYDROHALOGENATION

General Reaction:


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CONCEPT: ACID-CATALYZED HYDRATION

● Same reagents as acid-catalyzed dehydration, except starting with a _____________ __________ instead of an alcohol.

● Same as the general mechanism hydrohalogenation, except with _____________ as the nucleophile

● Remember that EVERY acid-cat. mechanism begins with ________________ and ends with ________________

General Reaction:


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PRACTICE: Provide the mechanism and predict the product of the following reaction.

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CONCEPT: OXYMERCURATION-REDUCTION

General Reaction:

Mechanism:

1. Electrophilic Addition

2. Nucleophilic Substitution (SN2)

3. Reduction (demurcuration)

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PRACTICE: Provide the mechanism and predict the product of the following reactions.

a.

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CONCEPT: HYDROBORATION-OXIDATION

General Reaction:

Mechanism:


2. Oxidation

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a.

b.

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CONCEPT: CATALYTIC HYDROGENATION AND WILKINSON’S CATALYST

General Reaction:

PRACTICE: Provide the products for the following reaction.

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CONCEPT: HALOGENATION

General Reaction:

Mechanism:



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CONCEPT: HALOHYDRIN FORMATION

General Reaction:

Mechanism:



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a.

b.

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CONCEPT: CYCLOPROPANATION

□ Carbenes are reactive intermediates. They are unstable because they violate the ___________ ___________.

□ There are 4 methods commonly used to introduce carbene intermediates:

1.

2.

3.

4.

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CONCEPT: EPOXIDATION

□ Epoxides are added to double bonds using _________________ ____________

● Common reagents are _____________ and ___________

Mechanism:

□ Epoxides can also be generated though an intramolecular _______ reaction of halohydrins.

Mechanism:

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CONCEPT: EPOXIDE RING OPENING

1. Acid-Catalyzed Ring Opening

Following protonation of the epoxide, the nucleophile will attack the side of the ring with the most ___________ character:

2. Base-Catalyzed Ring Opening

The strong nucleophile will attack the side of the ring that is ___________ substituted

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CONCEPT: SYN VICINAL DIHYDROXYLATION

General Reaction:

EXAMPLE: Predict the product for the following multi-step reaction.

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CONCEPT: WEAK OXIDATIVE CLEAVAGE

Ozonolysis: Ketones + Aldehydes + Formaldehyde

PRACTICE: Predict the products of the following reaction

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CONCEPT: OZONOLYSIS – FULL MECHANISM

The mechanism for ozonolysis proceeds through multiple intermediates.

●Ozonolysis is combined with either a reductive, or an oxidative workup

□ Reductive workup: S(CH3)2 or Zn/HOAc

□ Oxidative Workup: H2O2

Ozonolysis Mechanism:

Reductive Workup Mechanism:

Oxidative Workup Mechanism:

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PRACTICE: Predict the products and show the full mechanism for the following reaction

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CONCEPT: OXIDATIVE CLEAVAGE

Strong Oxidative Cleavage: Ketones + Carboxylic Acid + Carbon Dioxide

PRACTICE: Predict the product of the following reaction.

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CONCEPT: OXIDATIVE CLEAVAGE

Cleavage of Alkynes: Carboxylic Acid + Carbon Dioxide

EXAMPLE: Predict the product of the following reaction.

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CONCEPT: ALKYNE HYDROHALOGENATION

□ Alkynes react with some addition reagents in excess to produce double addition products.

● Keep in mind that _____________ carbocations CANNOT easily rearrange.

Hydrohalogenation of Alkynes

□ Product: __________________________

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CONCEPT: ALKYNE HALOGENATION

Halogenation

□ Product: __________________________

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CONCEPT: ALKYNE HYDRATION

□ Vinyl alcohols are uniquely reactive due to a phenomenon called tautomerization.

● They reversibly swap the positions of a ___________ and a _____ bond.

Oxymercuration of Alkynes

□ Product: __________________________

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Hydroboration of Alkynes

□ Product: __________________________

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organic - clutch ch. 10 - addition...

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