ORGANIC CHEMISTRY W/ST.GDE W/ACCESS
ORGANIC CHEMISTRY W/ST.GDE W/ACCESS
8th Edition
ISBN: 9780134892566
Author: Bruice
Publisher: PEARSON
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Chapter 28, Problem 35P
Interpretation Introduction

Interpretation:

The two product in the given reaction are formed after [1, 7] sigmatropic rearrangement, one due to hydrogen migration and the other to deuterium migration.  It should be represented the configuration of product by replacing the A and B with appropriate atoms (H or D)

Concept introduction:

In a sigmatropic reaction “ one new sigma-bond is formed as another breaks.”

ORGANIC CHEMISTRY W/ST.GDE W/ACCESS, Chapter 28, Problem 35P , additional homework tip  1

Sigma tropic rearrangement reactions are designated with digits.  For example a [1, 3] sigma tropic rearrangement describe a reaction in which the residue migrates from position 1 to position 3

Woodward –Hoffmann rules are the set of rules used to vindicate or predict certain aspects of the stereo chemical outcome and activation energy of pericyclic reactions.

Woodward – Hoffmann rules for sigma tropic rearrangement reactions are listed below

SumofthenumberofbondsinthereactingsytemsofbothreagentsReactionconditionsAllowedmodeofbond formationEvennumberThermalAntarafacialPhotochemicalSuprafacialOddnumberThermalSuprafacialPhotochemicalAntarafacial

Migration of carbon and hydrogen will occur in a sigmatropic rearrangement reaction.  Migration of hydrogen in suprafacial and antarafacial rearrangement can be represented as follows,

ORGANIC CHEMISTRY W/ST.GDE W/ACCESS, Chapter 28, Problem 35P , additional homework tip  2ORGANIC CHEMISTRY W/ST.GDE W/ACCESS, Chapter 28, Problem 35P , additional homework tip  3

Carbon migrating with one lobe of its p orbital interacting

ORGANIC CHEMISTRY W/ST.GDE W/ACCESS, Chapter 28, Problem 35P , additional homework tip  4 ORGANIC CHEMISTRY W/ST.GDE W/ACCESS, Chapter 28, Problem 35P , additional homework tip  5

Carbon migrating with both lobe of its p orbital interacting

ORGANIC CHEMISTRY W/ST.GDE W/ACCESS, Chapter 28, Problem 35P , additional homework tip  6ORGANIC CHEMISTRY W/ST.GDE W/ACCESS, Chapter 28, Problem 35P , additional homework tip  7

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Two products are formed in the following [1,7] sigmatropic rearrangement, one due to hydrogen migration and the other to deuterium migration. Showthe configuration of the products by replacing A and B with the appropriate atoms (H or D).
The reaction of butan-2-ol with concentrated aqueous HBr goes with partial racemization, giving more inversion thanretention of configuration. Propose a mechanism that accounts for racemization with excess inversion.(b) Under the same conditions, an optically active sample of trans-2-bromocyclopentanol reacts with concentrated aqueous HBr to give an optically inactive product, (racemic) trans-1,2-dibromocyclopentane. Proposea mechanism to show how this reaction goes with apparently complete retention of configuration, yet withracemization. (Hint: Draw out the mechanism of the reaction of cyclopentene with Br2 in water to give thestarting material, trans-2- bromocyclopentanol. Consider how parts of this mechanism might be involved in thereaction with HBr.)
When Br2 is added to buta-1,3-diene at -15 °C, the product mixture contains 60% ofproduct A and 40% of product B. When the same reaction takes place at 60 °C, theproduct ratio is 10% A and 90% B.Show why A predominates at -15 °C and B predominates at 60 °C.
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