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    Ioc 8

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    1. The document is a problem set from an organic chemistry class covering reactions involving heterocycles, electrocyclic reactions, photochemical and thermal reactions of compounds, Diels-Alder reactions, and ring-opening reactions. Students are asked to analyze reaction mechanisms, propose syntheses, and identify products. 2. The problem set is due on October 20 and contains 6 practice problems related to the course material covering pericyclic and named reactions. Students are asked to identify reaction types, draw structures, and analyze stereochemistry. 3. Additional practice problems are provided related to the exam covering pericyclic reactions, reaction products, and spectral analysis to identify functional groups and stereochemistry. Students are asked to identify

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    Ioc 8

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    Karthikeyan
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    1. The document is a problem set from an organic chemistry class covering reactions involving heterocycles, electrocyclic reactions, photochemical and thermal reactions of compounds, Diels-Alder reactions, and ring-opening reactions. Students are asked to analyze reaction mechanisms, propose syntheses, and identify products. 2. The problem set is due on October 20 and contains 6 practice problems related to the course material covering pericyclic and named reactions. Students are asked to identify reaction types, draw structures, and analyze stereochemistry. 3. Additional practice problems are provided related to the exam covering pericyclic reactions, reaction products, and spectral analysis to identify functional groups and stereochemistry. Students are asked to identify

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    IOC 8

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    1. The document is a problem set from an organic chemistry class covering reactions involving heterocycles, electrocyclic reactions, photochemical and thermal reactions of compounds, Diels-Alder reactions, and ring-opening reactions. Students are asked to analyze reaction mechanisms, propose syntheses, and identify products. 2. The problem set is due on October 20 and contains 6 practice problems related to the course material covering pericyclic and named reactions. Students are asked to identify reaction types, draw structures, and analyze stereochemistry. 3. Additional practice problems are provided related to the exam covering pericyclic reactions, reaction products, and spectral analysis to identify functional groups and stereochemistry. Students are asked to identify

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    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    48 views4 pages

    Ioc 8

    Uploaded by

    Karthikeyan
    1. The document is a problem set from an organic chemistry class covering reactions involving heterocycles, electrocyclic reactions, photochemical and thermal reactions of compounds, Diels-Alder reactions, and ring-opening reactions. Students are asked to analyze reaction mechanisms, propose syntheses, and identify products. 2. The problem set is due on October 20 and contains 6 practice problems related to the course material covering pericyclic and named reactions. Students are asked to identify reaction types, draw structures, and analyze stereochemistry. 3. Additional practice problems are provided related to the exam covering pericyclic reactions, reaction products, and spectral analysis to identify functional groups and stereochemistry. Students are asked to identify

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    of 4

    Massachusetts Institute of Technology

    Organic Chemistry 5.13

    October 13, 2006


    Prof. Timothy F. Jamison

    Problem Set #4

    Due Friday, October 20, 12:05 p.m., in lecture (before lecture)

    1. Treatment of compound 1 below with a strong base (e.g., n-BuLi) gives a heterocycle with a 5
    membered ring treatment with a weak acid (work-up). Account for the relative stereochemistry
    observed in the product.

    1
    n-BuLi
    HN N
    N N

    2. Propose a mechanism for the reaction below that involves a thermal 4π electrocyclic ring
    closure. Clearly indicate the relative stereochemistry in all intermediates.

    O O
    catalytic H+

    Me
    Me

    3. Based on the photochemical and thermal electrocyclic reactions of compound 2 below,


    comment on the nature of the π system in its 9-membered ring. Account for the relative
    stereochemistry observed in each of the two reactions.

    4. Heating compound 3 below at reflux in toluene in the presence of methyl acrylate affords two
    products, A and B in a 1:1 ratio of diastereomers. With a catalytic amount of base, A is
    converted to B. What are the structures of A and B? Clearly indicate the relative
    stereochemistry in each. Hint: A Diels-Alder reaction is involved in part of the mechanism.

    CN O
    + !
    A + B
    OMe
    3

    5. Using retrosynthetic analysis, propose a synthesis of the five molecules below using a Diels-
    Alder reaction in each case. Starting with the Diels-Alder reaction you decide to use, write your
    synthesis in the “forward” direction, showing all steps and reagents necessary.

    (a) (b) CH3 O (c) O (d) CH3 (e) O CH3


    H H
    CH2CH3 HO H3CO
    O OH OH
    H
    CH2CH3 OH H3CO
    O Ph HO
    H
    O O CH3 O

    6. Compound A undergoes a ring-opening reaction when heated at 100 °C, but no reaction occurs
    when C is subjected to the same conditions. Suggest a mechanism for the conversion of A to
    B, identify the type of reaction involved, and explain why C does not undergo a similar
    transformation.

    100 °C

    H H
    A B

    100 °C
    No reaction

    H H
    C

    Practice Problems for Exam 2. (You do not need to turn these in with your problem set.) Some of
    the following problems cover material that we will not have covered by the time Problem Set 4 is due.
    Not all of the problems on the exam will be like this, but they are representative of some of the ones you
    might encounter.

    For each of the following problems:

    i. Fill in the boxes with the predicted product or necessary starting material. Indicate
    relative stereochemistry and/or double bond geometry, where appropriate. If no reaction
    occurs, write “no reaction” and skip parts ii. and iii.
    ii. Classify each pericyclic reaction according to the Woodward-Hoffmann rules ([π4s + π2s]
    cycloaddition, e.g.).

    a.
    H3C H
    ! h"

    H3C H
    C10H16 C10H16

    b.
    H
    ! h"

    H
    ! h"

    c.
    O
    N !
    N

    CH3

    d.
    O O

    O O
    CH3
    O h" ! O

    ! !
    CH3

    O O

    O O
    CH3
    O h" ! O

    ! !
    CH3

    e.
    !
    CH3
    O

    f.

    H3C ! Hint: A 1H NMR spectrum of the product indicates


    H 2 CH3 singlets,1 CH3 doublet, and 3 alkene protons.
    CH3
    C7H12

    g.
    D
    O CH3 !
    Note: D = deuterium (2H).
    CH3
    D

    h.

    CH2 O
    1. MgBr
    C + h! H
    CH2
    2. HCl, H2O
    (allene) H

    O
    KH H+
    "

    C11H16O
    H

    Note: The brackets indicate that Note: A 13C NMR spectrum of this
    the product of the reaction with compound shows 11 signals: one
    potassium hydride is not isolated, at 208.2 ppm, 4 between 100 and
    but rather rapidly converted to the 150 ppm, and 6 between 10 and 50
    next structure after treatment with acid. ppm.

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