14 Conjugation, Resonance, Dienes

Date Started @February 15, 2021

Status

Unit/Module Chapter 14

Week 3

14 CONJUGATION, RESONANCE, DIENES

Conjugation
- occurss whenever orbitals overlap on three or more adjacent atoms.
- having three or more p orbitals on adjacent atoms allows p orbitals to overlap and electrons to delocalized— electron density in two 𝜋
bonds
- when p orbitals overlap, electron denisty in each of 𝜋 bond is spread out over larger volume → lowering the energy of molecule →
more stable
Common Conjugated Systems:

1,3-dienes

allylic carbocations

Conjugation: 1,3 - Dienes

- two carbon-carbon double bonds joined by by a single bond
- each C-atom is bonded to three other atoms and has no nonbonded electron pairs
- each carbon atom is sp² and has one p orbital containing electron
- four p orbitals on adjacent atoms make 1,3-dienes a conjugated system
Isolated Dienes
- compound ahving two double bonds separated by more than one σ bond
- 𝜋 bonds are too far apart to be conjugated, and thus electrons are localize— electron density in 𝜋 bonds between two carbon atoms
(unlike in conjugated system, electron density os delocalized over four atoms.

Conjugation: Allylic Carbocations

- another sample of conjugated system
- three C-atoms of allyl carbocation— one positively charged atom & two carbon forming double bonds— are sp² hybridized and have
an unhybridized p orbital
- each p orbital of double bonded carbons has an electron, but the p orbital of carbocation do not.

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 - three p orbital on three adjacent atom, even cabocation's empty, make the it conjugated
- conjugation stabilizes allyl carbocation because of overlapping of three adjacent p orbitals delocalizing the electron density of 𝜋
bonds of three atoms

Resonance and Allylic Carbocations

Resonance Structures
- two or more different lewis structure with similar arrangement of atom
- two resonance differ in the placement of 𝜋 bond and nonbonded electrons, but placement of atoms & σ bonds stays the same

Stability of Allylic Carbocation

Conjugated Allyl Carbocation
- sample of a species for which two resonance structures can be drawn— which illustrates how conjugation delocalized electrons
Hybrid Allyl Carbocation & Stability
- true structrure of allyl carbocation
- positive charge is delocalized over two terminal carbons
- delocalizing electron density lowers the energy of the hybrid, thus stabalizing allyl carbocation making it more stable than
normal methyl

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 Allylic Carbocation in Biological Reactions
- formed from diphosphates
- key intermediated in variety of bioligical reactions— synthesis of geranyl diphosphate from two five-carbon substrates: dimethyl
diphoaphate and isopentyl diphosphate.

- a biological process that resulst in formation of new C—C bond and involves two key steps— loss of good LG (diphospahte, P₂O₇⁴⁻ or
PPᵢ) → allylic carbocation, followed by Nu:⁻ attack with electron-rich double bond

Biological Formation of Geranyl Diphosphate:

[1] loss of diphosphate leaving group → allylic carbocation
[2] Nucleophilic attack of [double bond of] isopentyl diphosphate on allylic carbocation → C—C σ bond
[3] deprotonation by general base → geranuyl diphosphate

Commom Examples of Resonance

Resonance
- involves delocalization of 𝜋 bonds and non-bonded electrons
Four Common Bonding Patterns
→ Three-Atom "Allyl" System
→ Conjugated double bonds
→ Cations with a Positive Charge Adjacent to a Lone Pair
→ Double Bonds with One Atom more Electronegative than the other

Type [1] Three-Atom "Allyl" System

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 - any group of three atoms with a double bond X=Y and an Z atom containing p orbital with zero to two electrons → two resonance
structures are possible
→ X, & Z can be all carbon atoms or heteratoms; atom Z bonded to multiple bond canr be charged or neutral

- an allyl type resonance because it can be drawn for allylic carbocations/-anion and allylic radicals

Type [2] Conjugated double bonds

- cyclic conjugated rings → two resonance structures

- conjugated dienes → three resonance structures (two structures involve charge separation)

Type [3] Cations with a Positive Charge Adjacent to a Lone Pair

- lone pair & positive charge are adjacent atoms → two resonance structures
- overall charge is the same in both structures

Type [4] Double Bonds with One Atom more Electronegative than the other
- double bond X=Y in which electronegativity of Y> X → two resonance structure
- movement of 𝜋 electrons onto

Resonance Hybrid
- combination of all its valid resonance structures
- more closely resembles the best resonance structure— major contributor to the hybrid and the rest are minor contributors

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 - lower its energy, more a resonance structure contributes to overall structure of hybrid
Rules to Evaluate Relative Energies of Valid Resonance Structures

[1] more bonds & fewer charges are better

[2] every atom has an octet are better
[3] placing a negative charge on a more electronegative atom are better

Electron Delocalization, Hybridization and Geometry

- to delocalize nonbonded electrons / electrons in 𝜋 → there must be p orbitals that can overlap; hybridization of an atom is different
than that would have been predicted
- delocalizing electrons stabilizes a molecule.

- in a system X=Y—Z:, Z is sp² hybridized & the nonbonded electron pair occupies a p orbital to make a system conjugated

Conjugated Dienes
Polyenes
- compounds with many 𝜋 bonds

1,3-dienes
- conjugated diene— compounds with two adjacent double bonds joined by one σ bond
- three possible stereoisomers (discrete molecules)

trans, trans-1,3-diene / E,E-1,3-diene

cis,cis-1,3-diene / Z,Z-1,3-diene

cis,trans-1,3-diene / Z,E-1,3-diene

- two possible conformation (interconverts)—rotation of C—C bonds joining two double bonds

s-cis conformation
- two double bonds on the same side of single bond

s-trans conformation
- two double bonds on opposite sides of single bonds

📌 stereoisomers are different compounds where groups on each end of a C—C double bond are arranged differently

📌 two conformation are same compound which interconvert by bond rotation

Interesting Dienes and Polyenes

Isoprene
- given off by plants as temperature rises— process thought to increase a plant's tolerance for heat stress

Lycopene
- naturally occuring molecule responsible for the red color of tomatoes— 11 conjugated double bonds— and other fruits, an antioxidant
like vitamine E.

Simvastatin & Calcitriol

- has conjugated double bonds in addition to other functional groups
- (simvastatin) the generic name for Zocor: cholesterol-lowering medicine
- (calcitriol) biologically active hormone formed from vitamin D₃ obtained in diet- regulates calcium an phosphorous metabolism.

Carbon—Carbon σ Bond Length

Four Features in Conjugated dienes from isolated dienes:

[1] C—C sigle bond joining two double bonds is unusually short

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 - single bond is formed by overlap of two sp² hybridized orbitals
- Csp²—Csp² bond should be shorter than Csp³—Csp³ bond because of the formation of orbitals having a higher percent s-character
[2] conjugated dienes are more stable than similar isolated dienes

[3] some reactions of conjugated dienes are different than reactions of isolated double bonds
[4] conjugated dienes absorb longer wavelengths of UV light

Stability of Conjugated Dienes

Heat of Hydrogenation (𝚫Hº)
- addition of hydrogen that gives off heat in the reaction
- use to measure alkene stability
- more stable diene has smaller heat of hydrogenation
- a conjuagted diene has smaller heat of hydrogen and more stable that similar isolated diene
- less energy released → more stable

Electrophilic Addition: 1,2- versus 1,4-Addition

Addition
- occur in conjugated dienes giving a mixture of products
- conjugated dienes undergo a unique addition reaction not seen in alkenes or isolated dienes

HX adds to alkenes to form alkyl halides (R-X)

in isolated dienes, electrophilic addition of one equivalent of HBr yields one product and Markovnikov's rule—H attaches to
less substituted carbon—is followed

in conjugated diene, electrophilic addition of one equivalent of HBr yields two products; because of the resonance-stabilized
allylic carbocation intermediate

1,2-addition product result from Markovnikov addition of HBr across two adjacent atoms of diene

1,4-addition product results from addition of HBr to two end carbons of diene—conjugate addition

Electrophilic Addition of HBr to a 1,3-Diene—1,2- and 1,4-addition

[1] Protonation of terminal carbon of 1,3-diene from HBr → resonance-stabilized allylic carbocation
[2] Nu:⁻ attack of Br⁻ occur at either site of resonance-stabilize carbocation that bears (+) → 1,2- and 1,4-addition products

Kinetic Versus Thermodynamic Products

amount of formation of following products depends greatly on the reaction conditions:

1,2-addition product: favors low temperature: Kinetic(-ally stable) Product; formed faster
→ it is a kinetic product because of the proximity effect— Br⁻ is closer to adjacent carbon (C2) that it is to C4.

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 1,4-addition product: favors high-temperature: Thermodynamic(-ally stable) Product; must be more stable because
predominates equilibrium
→ more stable beacause it has two alkyl groups bonded to the C—C double bond (disubstituted alkene), where as 1,2-product has
only one (monosubstituted)

- in this electrophilic additonof HBr, the more stable product is formed more slowly
→ rate of reaction is determined by its energy of activation (Ea),
→ amount of product present at equilibrium is determined by its stability
why is it temperature dependent:

→ at low temp, energy activation is more important factor, since molecules do not have enough kinetic energy to overcome the
higher energy barrier at low temp.
→ at higher temp, most molecules have enough kinetic energy to reach either transition state— two products are in equilibrium but
the more stable compound—lower in energy— is the major product.

Diels-Alder Reaction
- named for a german chemisr Otto Diels and Kurt Alder
- addition reaction betweet 1,3-diene & an alkene called dienophile → new six membered ring

- three curved arrows are needed to demonstrate the cyclic movement of electron pairs— can be drawn clockwise or counter clockwise
— because three 𝜋 bonds break → two σ bonds and one 𝜋 bond is formed
Diels-Alder Reaction Common Features:
[1] initiated by hear → a thermal reaction
[2] forms a new six-membered ring
[3] three 𝜋 bonds break → two σ bonds and one 𝜋 bond is formed
[4] concerted— all bonds are broken and formed at a single step
Drawing the products of a Diels-Alder Reaction

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 [1] arrange diene & dienophile next to each other, diene in s-cis conformation
[2] cleave three bonds and use arrows to show where new bonds will form

Specific Rules Governing Diels-Alder Reaction

Diene Reactivity
[1] diene can react only when it adopts the s-cis conformation
- both ends of conjugated diene should be close to 𝜋 bond of dienophile for reaction to occur, thus rotation of s-trans conformation
on C—C σ bond must occur before reaction can take place
- when two double bonds are contrained in s-cis conformation, it gets unusually reactive
- when two double bonds are constrained in s-trans conformation, it is unreactive

Dienophile Reactivity
[2] electron withdrawing substituents in dienophile increase the reaction rate
- strong electrophile (dienophile) → more reactive
Common Dienophiles:

Stereospecificity
[3] stereochemostry of dienophile is retained in the product

cis dienophile → cis-substituted cyclohexene (achiral (solid-solid, dashed-dashed) meso compound)

trans dienophile → tran-stubstituted cyclohxene (enantionmers (dashed-wedged, mirror)

cyclic dienophile → bicyclic product (fused ring system) → cis-H dienophile, cis-H in product

Rule of Endo Addition

[4] when endo and exo product are possible, the endo product is preferred
→ endo product is the major product, allowing more interaction between electron-rich diene & electron-withdrawing substituent Z on
dienophile
- when cyclic diene react with dienophile → six-membered ring & above the ring there is an one atom "bridge"— originated as sp³
hybridized carbon od dienes that was not involved in the reaction

- a bicyclic system ring in which two rings share non-adjacent atoms is a bridge ring system
→ a substituent on one bridge is endo if it is closer to the longer bridge that joins the carbons common to both rings
→ a substituent is exo if it is closer to shorter bridge that joins the carbosn together

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 Other things about Diels-Alder Reaction
drawing starting materials from Diels-Alder adduct— product of a direct addition

locate six-membered ring containing the C=C

draw three arrows around ring, beginning with 𝜋 bond. Each arrow moves two electrons to adjacent bond, cleaving one 𝜋 and two
σ bonds → three 𝜋 bonds

retain stereochemistry of substituents on the C=C of dienophile. Cis substituents on six-membered ring give a cis dienophile

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 Retro Diel-Alder Reaction
Cyclopenta-1,3-diene
- a reactive diene which readily undergoes a diel-alder reactopm with itslelf; cyclopenta-1,3-diene dimerizes because one molecule acts
as the diene, the other acts as dienophile
- a rapid reaction at room temperature only to completely dimeriz

Conjugated Dienes and Ultraviolet Light

ULTRAVIOLETLIGHT ABSORPTION (high energy, high frequency, low wavelength)

- Absorption of UV light by a molecule can promote an electron from lower energy state to a higher one, ground to excited
state; useful at 200-400nm
- with conjugated dienes, the energy difference between ground & excited states decreases, so longer wavelengths of light can be
used to promote electrons
- molecules having eight or more conjugated 𝜋 bonds with absorption shifts from UV to visible region: compound takes on color
of the light it does not absorb

more conjugated double bonds higher wavelength

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