Chapter 26: Q 41. (page 1072)
Devise a synthesis of (E)-1-phenylhex-1-ene ( ) using hydrocarbons having 鈮 6 C鈥檚 and a Suzuki reaction as one of the steps.
Short Answer
Answer
Mechanism of (E)-1-phenylhex-1-ene synthesis
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Chapter 26: Q 41. (page 1072)
Devise a synthesis of (E)-1-phenylhex-1-ene ( ) using hydrocarbons having 鈮 6 C鈥檚 and a Suzuki reaction as one of the steps.
Answer
Mechanism of (E)-1-phenylhex-1-ene synthesis
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Metathesis reactions can be carried out with two different alkene substrates in one reaction mixture. Depending on the substitution pattern around the C=C, the reaction may lead to one major product or a mixture of many products. For each pair of alkene substrates, draw all metathesis products formed. (Disregard any starting materials that may also be present at equilibrium.) With reference to the three examples, discuss when alkene metathesis with two different alkenes is a synthetically useful reaction.

The reaction of cyclohexene with iodo-benzene under Heck conditions forms E, a coupling product with the new phenyl group on the allylic carbon, but none of the 鈥渆xpected鈥 coupling product F with the phenyl group bonded directly to the carbon鈥揷arbon double bond.
a. Draw a stepwise mechanism that illustrates how E is formed.
b. Step [2] in Mechanism 26.2 proceeds with syn addition of Pd and R' to the double bond.What does the formation of E suggest about the stereochemistry of the elimination reaction depicted in Step [3] of Mechanism 26.2?

Draw the product formed from the ring-closing metathesis of each compound. Then, devise a synthesis of each metathesis starting material from benzene, alcohols with less than five carbons, and any needed organic and inorganic reagents.
a.

b.

What product is formed by ring-closing metathesis of each compound?
a.

b.

Sulfur ylides, like the phosphorus ylides of Chapter 21, are useful intermediates in organic synthesis. Methyl trans-chrysanthemate, an intermediate in the synthesis of the insecticide pyrethrin I (Section 26.4), can be prepared from diene A and a sulfur ylide. Draw a stepwise mechanism for this reaction.

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