Alkene Reaction Summary Sheet PDF

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Summary

alkene reaction summary sheet for ch. 8...

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The following are the summarized reactions of alkenes. For reactions marked with an asterisk (*) you need to know and understand the mechanism, for the rest you only need to know everything else.

Starting Material

Reaction

Reagents

Hydrohalogenation

HX X= Cl, Br, I

Halogenation

Halohydrin formation

Bromohydrin formation

X2, CCl4 X= Cl, Br

X2, H2O X= Cl, Br

NBS, H2O, DMSO

Alkene Reaction Summary Sheet Markovnikov Anti/Syn AntiStereochemistry Markovnikov Markovnikov H adds to less Addition* NA subs. C X adds to more subs. C

General Mechanism

Addition*

Addition*

Addition*

+

Hydration: Acid Catalyzed

H2O, H3O cat. = H3PO4, H2SO4

Addition*

NA

Markovnikov-ish X adds to less subs. C OH adds to more subs. C

Anti Addition: each X adds on opposite sides of the C=C plane

Anti Addition: X adds on one sides of the C=C plane, OH adds on the other side

Stereo-specificity

Product/s

X NA

+ en.

H Cis/Z gives syn (cis) dihalides (wedge-wedge or dash-dash on a zigzag chain)

X + en.

Trans/E gives anti (trans) dihalides(wedgedash or dash-wedge on a zigzag chain) Cis/Z gives syn (cis) halohydrin (wedge-wedge or dash-dash on a zigzag chain)

X

HO + en.

Markovnikov-ish Br adds to less subs. C OH adds to more subs. C

Anti Addition: Br adds on one sides of the C=C plane, OH adds on the other side

Markovnikov H adds to less subs. C OH adds to more subs. C

NA

CHEM!227!!(!C.!SERRANO!LUGO!

Trans/E gives anti (trans) halohydrin (wedge-dash or dash-wedge on a zigzag chain) Cis/Z gives syn (cis) halohydrin (wedge-wedge or dash-dash on a zigzag chain)

X

HO + en

Trans/E gives anti (trans) halohydrin (wedge-dash or dash-wedge on a zigzag chain)

Br

HO NA

+ en

H

Starting Material

Reaction

Reagents

Hydration: Oxymercuration Demercuration

1. Hg(OAc)2, H2O 2. NaBH4

Ether formation: Oxymercuration Demercuration

Hydration: Hydroboration Oxidation Reduction: Hydrogenation

Oxidation: Epoxidation

1. Hg(OAc)2, ROH 2. NaBH4

1. BH3 2. H2O2, NaOH

H2, Pd/C

mCPBA

General Mechanism

Addition*

Addition*

Addition* Mechanism for step 1

Addition*

Markovnikov AntiMarkovnikov Markovnikov H adds to less subs. C OH adds to more subs. C Markovnikov H adds to less subs. C OH adds to more subs. C Anti-Markovnikov OH adds to less subs. C H adds to more subs. C

NA

Addition*

NA

Epoxidation: Reaction of Bromohydrin and a strong base

1. Br2, H2O 2. NaOH or NaH

Addition followed by Substitution*

NA

Dihydroxylation: Epoxidation followed by Acid Hydrolysis

1. mCPBA + 2. H3O , H2O

Addition followed by Substitution*

NA

Anti/Syn Stereochemistry Anti Addition: H adds on one sides of the C=C plane, OH adds on the other side Anti Addition: H adds on one sides of the C=C plane, OH adds on the other side Syn Addition: H and OH add on the same side of the C=C plane Syn Addition: Both H add on the same side of the C=C plane

Syn Addition: Epoxide can only be formed if C-O-C bond are all on the same side

Follows Anti Addition of Bromohydrin formation Substitution inverts the stereochemistry of the C bonded to OH Follows Syn Addition of Epoxide formation Substitution inverts the stereochemistry of the more substituted C

CHEM!227!!(!C.!SERRANO!LUGO!

Stereo-specificity

Product/s

HO NA

+ en

H RO NA

+ en

H

H NA

+ en

OH NA

H + en

H Subs. that are Cis/Z in the orig. alkene will remain syn/cis in the product Subs. that are Trans/E in the orig. alkene will remain anti/trans in the product

O + en

H

O NA

+ en

H

HO NA

+ en

OH

Reaction Starting Material

General Mechanism

Reagents

Epoxide Opening with HX

1. mCPBA 2. HX X= Cl, Br, I

Addition followed by Substitution

Markovnikov AntiMarkovnikov

Anti/Syn Stereochemistry

NA

Follows Syn Addition of Epoxide formation Substitution inverts the stereochemistry of the more substituted C

Dihydroxylation: Oxidation with OsO4

1. OsO4 2. NaHSO3, H2O

Addition* Mechanism of step 1

NA

Ozonolysis

1. O3 2. Zn, HOAc H2O

Complicated: Multiple Mechanisms

NA

Dihydroxylation followed by Oxidative Cleavage

1. OsO4 2. NaHSO3, H2O 3. HIO4

Oxidative Cleavage by Permanganate

KMnO4, H3O

Addition followed by Rearrangement Addition followed by Rearrangement

Oxidative Cleavage by Ozonolysis in Peroxide

Cyclopropanation: Reaction with Dichlorocarbene

Cyclopropanation Reaction with Carbenoid Aka SimmonsSmith reaction

+

1. O3 + 2. H2O2

Complicated: Multiple Mechanisms

CHCl3, KOH

Addition

X NA

+ en

OH Subs. that are Cis/Z in the orig. alkene will remain syn in the zigzag chain

HO + en

Subs. that are Trans/E in the orig. alkene will remain anti in the zigzag chain

OH

NA

NA

O

H NA

NA

NA

NA

NA

! !

Product/s

O

Addition CH2I2, Zn(cu)

Syn Addition: Both OH add on the same side of the C=C plane

Stereo-specificity

O

Dihydroxylation step follows Syn Addition

NA

Reaction with KMnO4 follows Syn Addition

NA

Reaction with KMnO4 follows Syn Addition

NA

Syn Addition: Cyclopropane can only be formed if C-C-C bond are all on the same

Syn Addition: Cyclopropane can only be formed if C-C-C bond are all on the same

CHEM!227!!(!C.!SERRANO!LUGO!

O

H O

Subs. that are Cis/Z in the orig. alkene will remain syn/cis in the product Subs. that are Trans/E in the orig. alkene will remain anti/trans in the product

OH O

O

OH

O

Cl Cl + en

H

Same as the CHCl3 KOH rxn

+ en

H

The following are the summarized reactions of alkenes. For reactions marked with an asterisk (*) you need to know and understand the mechanism, for the rest you only need to know everything else.!

Starting Material

Reaction

Reagents

Hydrohalogenation

HX X= Cl, Br, I

Halogenation

Halohydrin formation

Bromohydrin formation

X2, CCl4 X= Cl, Br

X2, H2O X= Cl, Br

NBS, H2O, DMSO

Alkene Reaction Summary Sheet Markovnikov Anti/Syn AntiStereochemistry Markovnikov

General Mechanism

Addition*

Addition*

Addition*

Addition*

+

Hydration: Acid Catalyzed

Hydration: Oxymercuration Demercuration

H2O, H3O cat. = H3PO4, H2SO4

1. Hg(OAc)2, H2O 2. NaBH4

Addition*

Addition*

Markovnikov H adds to less subs. C X adds to more subs. C

NA

NA

Anti Addition: each X adds on opposite sides of the C=C plane

Stereo-specificity

Product/s

NA

X

H

Cis/Z gives syn (cis) dihalides + en Trans/E gives anti (trans) dihalides

X

X

Cis/Z gives syn (cis) halohydrin

Markovnikov-ish X adds to less subs. C OH adds to more subs. C

Anti Addition: X adds on one sides of the C=C plane, OH adds on the other side

Markovnikov-ish Br adds to less subs. C OH adds to more subs. C

Anti Addition: Br adds on one sides of the C=C plane, OH adds on the other side

Markovnikov H adds to less subs. C OH adds to more subs. C

NA

Markovnikov H adds to less subs. C OH adds to more subs. C

Anti Addition: H adds on one sides of the C=C plane, OH adds on the other side

Trans/E gives anti (trans) halohydrin Both wedge-dash or dash-wedge on a ring Cis/Z gives syn (cis) halohydrin

+ en

OH

Trans/E gives anti (trans) halohydrin Both wedge-dash or dash-wedge on a ring

+ en

OH

CHEM!227!!(!C.!SERRANO!LUGO!

Br

NA

OH

! !

X

H

NA

OH H

Starting Material

General Mechanism

Markovnikov AntiMarkovnikov

1. Hg(OAc)2, ROH 2. NaBH4

Addition*

Markovnikov H adds to less subs. C OH adds to more subs. C

1. BH3 2. H2O2, NaOH

Addition* Mechanism of Step 1

Reaction

Reagents

Ether formation: Oxymercuration Demercuration

Hydration: Hydroboration Oxidation

Reduction: Hydrogenation

H2, Pd/C

Addition*

Anti/Syn Stereochemistry Anti Addition: H adds on one sides of the C=C plane, OH adds on the other side

Stereo-specificity

Product/s

NA

OR H

Anti-Markovnikov OH adds to less subs. C H adds to more subs. C

Syn Addition: H and OH add on the same side of the C=C plane

NA

NA

Syn Addition: Both H add on the same side of the C=C plane

NA

+ en

OH

H

H

Oxidation: Epoxidation

Epoxidation: Reaction of Bromohydrin and a strong base

mCPBA

1. Br2, H2O 2. NaOH or NaH

Dihydroxylation: Epoxidation followed by Acid Hydrolysis

1. mCPBA + 2. H3O , H2O

Epoxide Opening with HX

1. mCPBA 2. HX X= Cl, Br, I

Addition*

Addition followed by Substitution*

Addition followed by Substitution*

Addition followed by Substitution*

NA

Syn Addition: Epoxide can only be formed if C-O-C bond are all on the same side

+ en Subs. that are Trans/E in the orig. alkene will remain anti/trans in the product

NA

Follows Anti Addition of Bromohydrin formation Substitution inverts the stereochemistry of the C bonded to OH

NA

NA

Follows Syn Addition of Epoxide formation Substitution inverts the stereochemistry of the more substituted C

NA

Follows Syn Addition of Epoxide formation Substitution inverts the stereochemistry of the more substituted C

NA

NA

! ! CHEM!227!!(!C.!SERRANO!LUGO!

H

Subs. that are Cis/Z in the orig. alkene will remain syn/cis in the product

O

+ en

O + en

OH OH

+ en

X

OH

Starting Material

Reaction

Reagents

General Mechanism

Markovnikov AntiMarkovnikov

Dihydroxylation: Oxidation with OsO4

1. OsO4 2. NaHSO3, H2O

Addition* Mechanism of Step 1

NA

Anti/Syn Stereochemistry

Syn Addition: Both OH add on the same side of the C=C plane

Stereo-specificity

Product/s

NA

+ en

OH OH O Ozonolysis

Dihydroxylation followed by Oxidative Cleavage Oxidative Cleavage by Permanganate Oxidative Cleavage by Ozonolysis in Peroxide

Cyclopropanation: Reaction with Dichlorocarbene Cyclopropanation Reaction with Carbenoid

1. O3 2. Zn, HOAc H2O 1. OsO4 2. NaHSO3, H2O 3. HIO4

KMnO4, H3O

+

Complicated: Multiple Mechanisms Addition followed by Rearrangement Addition followed by Rearrangement

NA

NA

H

NA

O O NA

Dihydroxylation step follows Syn Addition

H

NA

O O NA

Reaction with KMnO4 follows Syn Addition

OH

NA

O O

1. O3 + 2. H2O2

CHCl3, KOH

CH2I2, Zn(cu)

Complicated: Multiple Mechanisms

Addition

Addition

aka SimmonsSmith reaction

NA

Reaction with KMnO4 follows Syn Addition

OH

NA

O

NA

NA

Syn Addition: Cyclopropane can only be formed if C-C-C bond are all on the same

NA

Syn Addition: Cyclopropane can only be formed if C-C-C bond are all onhe same

NA

!

! ! CHEM!227!!(!C.!SERRANO!LUGO!

+ en

Cl Cl

+ en

The following are the summarized reactions of alkynes. This table does not include the reactions that produces alkynes, which are included in the exam.

Starting Material

Reaction

Reagents

Hydrohalogenation

HX X= Cl, Br, I

Halogenation

X2, CCl4 X= Cl, Br

Alkene Reaction Summary Sheet General Markovnikov Mechanism Anti-Markovnikov Addition

Addition

Hydration: Oxymercuration Demercuration

HgSO4, H2SO4 H2O

Addition

Hydration: Hydroboration Oxidation

1. BH3 2. H2O2, NaOH

Addition

Anti/Syn Stereochemistry

X

Markovnikov H adds to less subs. C X adds to more subs. C

NA

NA

Anti Addition: each X adds on opposite sides of the triple and double bond Gives trans st dihalides with the 1 equiv

Markovnikov H adds to less subs. C OH adds to more subs. C Anti-Markovnikov OH adds to less subs. C H adds to more subs. C

X

O

NA

Reduction: Cis Hydrogenation

H2 Lindlar catalyst

Addition

NA

Syn Addition

Reduction: Trans Hydrogenation

Li or Na NH3

Addition: single and two electron mechanism

NA

Trans Addition

1. O3 2. Zn, HOAc H2O

Complicated: Multiple Mechanisms

NA

NA

KMnO4

Addition

Acetylide formation followed by alkylation

X X O

Syn Addition: but inconsequential

Addition

Oxidative Cleavage using KMnO4

X

NA

H2, Pd/C

Ozonolysis

X

.

Syn Addition: but inconsequential since final product is an alkane

Reduction: Hydrogenation

Product/s

H

O CO2

OH O NA

NA

CO2

OH NaNH2, o RX (1 )*

Deprotonation of terminal alkyne, followed by substitution

NA

! o o *!If you use a 2 or 3 RX then elimination reaction will be preferred over ! substitution

! CHEM!227!!(!C.!SERRANO!LUGO!

NA

R

The following are the summarized reactions of alkynes. This table does not include the reactions that produce alkynes, which are included in the exam.

Starting Material

Reaction

Reagents

Hydrohalogenation

HX X= Cl, Br, I

Halogenation

Addition

Addition

Anti/Syn Stereochemistry NA

NA

Anti Addition: each X adds on opposite sides of the triple and double bond Gives trans st dihalides with the 1 equiv

Markovnikov H adds to less subs. C OH adds to more subs. C Anti-Markovnikov OH adds to less subs. C H adds to more subs. C

HgSO4, H2SO4 H2O

Addition

Hydration: Hydroboration Oxidation

1. BH3 2. H2O2, NaOH

Addition

Reduction: Hydrogenation

H2, Pd/C

Addition

NA

Syn Addition: but inconsequential since final product is an alkane

Reduction: Cis Hydrogenation

H2 Lindlar catalyst

Addition

NA

Syn Addition

Reduction: Trans Hydrogenation

Li or Na NH3

Addition: single and two electron mechanism

NA

Trans Addition

1. O3 2. Zn, HOAc H2O

Complicated: Multiple Mechanisms

NA

NA

Oxidative Cleavage using KMnO4

Product/s .!

Markovnikov H adds to less subs. C X adds to more subs. C

Hydration: Oxymercuration Demercuration

Ozonolysis

!

X2, CCl4 X= Cl, Br

Alkene Reaction Summary Sheet General Markovnikov Mechanism Anti-Markovnikov

X X X X

Br

X X

Br after 1 equiv. of X2

O

O

O

O

NA

Syn Addition: but inconsequential

O

O OH

O KMnO4

Addition

X X

after 2 equiv. of X2

NA

OH O

NA

OH

OH

The following are the summarized reactions of alkynes. This table does not include the reactions that produce alkynes, which are included in the exam.

Starting Material

Reaction

Reagents

Hydrohalogenation

HX X= Cl, Br, I

Halogenation

Addition

Addition

Anti/Syn Stereochemistry NA

NA

Anti Addition: each X adds on opposite sides of the triple and double bond Gives trans st dihalides with the 1 equiv

Markovnikov H adds to less subs. C OH adds to more subs. C Anti-Markovnikov OH adds to less subs. C H adds to more subs. C

HgSO4, H2SO4 H2O

Addition

Hydration: Hydroboration Oxidation

1. BH3 2. H2O2, NaOH

Addition

Reduction: Hydrogenation

H2, Pd/C

Addition

NA

Syn Addition: but inconsequential since final product is an alkane

Reduction: Cis Hydrogenation

H2 Lindlar catalyst

Addition

NA

Syn Addition

Reduction: Trans Hydrogenation

Li or Na NH3

Addition: single and two electron mechanism

NA

Trans Addition

1. O3 2. Zn, HOAc H2O

Complicated: Multiple Mechanisms
...