Organic Chemistry 6th Edition solutions

Organic Chemistry 6
What is the product of the following reaction? + Pd(0) OTf CO2Et n-Bu3Sn N O O N

Organic Chemistry 6
What sequence of reactions will produce the following product if starting with trimethylsilyl acetylene and the appropriate two aryl iodides? O O

Organic Chemistry 6
Show the product of the following reaction. O O nucleophilic carbene catalyst

Organic Chemistry 6
As has been demonstrated in the text, when the starting alkene has CH2 as its terminal group, the Heck reaction is highly stereoselective for formation of the E isomer. Here, the benzene ring is abbreviated C6H5!. Show how the mechanism proposed in the text allows you to account for this stereoselect

Organic Chemistry 6
The following reaction involves two sequential Heck reactions. Draw structural formulas for each organopalladium intermediate formed in the sequence and show how the fi nal product is formed. Note from the molecular formula given under each structural formula that this conversion corresponds to a los

Organic Chemistry 6
Complete these Heck reactions. O Pd(OAc)2, 2 Ph3P (CH3CH2)3N (a) 2 C6H5CH"CH2 1 I I Pd(OAc)2, 2 Ph3P (CH3CH2)3N (b) CH2"CHCOCH3 1

Organic Chemistry 6
Treatment of cyclohexene with iodobenzene under the conditions of the Heck reaction might be expected to give 1-phenylcyclohexene. The exclusive product, however, is 3-phenylcyclohexene. Account for the formation of this product. 3-Phenylcyclohexene (racemic) 1-Phenylcyclohexene (not formed) Pd(OAc)2

Organic Chemistry 6
Account for the formation of the product and for the cis stereochemistry of its ring junction. (The function of silver carbonate is to enhance the rate of reaction.) I Pd(OAc)2, PPh3 Ag2CO3, CH3CN COOMe COOMe H 86%

Organic Chemistry 6
Account for the formation of the following product, including the cis stereochemistry at the ring junction. TfO Pd(OAc)2, (R)-BINAP K2CO3 R R H

Organic Chemistry 6
The aryl diene undergoes sequential Heck reactions to give a product with the molecular formula C15H18. Propose a structural formula for this product. (C15H19I) C15H18 CH3CN 1% mol Pd(OAc)2 4% mol Ph3P I

Organic Chemistry 6
Heck reactions take place with alkynes as well as alkenes. The following conversion involves an intramolecular Heck reaction followed by an intermolecular Heck. Propose structural formulas for the palladium-containing intermediates involved in this reaction. Me COOMe MeOOC Me Heck reaction +

Organic Chemistry 6
The following conversion involves sequential Heck reactions. Propose structural formulas for the palladium-containing intermediates involved in this reaction. I EtOOC EtOOC SiMe3 SiMe3 Heck reaction EtOOC EtOOC

Organic Chemistry 6
The following transformation involves a series of four consecutive Heck reactions and the formation of the four-ring steroid nucleus (Section 26.4) as a racemic mixture. Propose structural formulas for the palladium-containing intermediates involved in this reaction. EtOOC EtOOC I Heck reaction EtOOC

Organic Chemistry 6
Show the sequence of Heck reactions by which the following conversion takes place. Note from the molecular formula given under each structural formula that this conversion corresponds to a loss of H and I from the starting material. (C14H17I) (C14H16) I 1% mol Pd(OAc)2 4% mol Pd3P

Organic Chemistry 6
Write the product of the following reaction and account for the regiochemistry that you predict. AcO OCH3 PdCl2 O SO2PH CO2CH3

Organic Chemistry 6
Write the steps that are critical in the following reaction in order to explain the stereo chemical outcome at the carbon marked with the asterisk. Pd(PPh3)4 NaCH(CO2CH3)2 H3C H2C CH3 * CO2CH3 CO2H CH3O2C O O

Organic Chemistry 6
One of the most useful aspects of Pd(0)-catalyzed allylic alkylation is the ability to take racemic mixtures of reactants and create preferred chirality in the product by the addition of a chiral ligand for the Pd metal. Draw the h3 -allylic complex created in the catalytic cycle of the following rea

Organic Chemistry 6
Another useful aspect of Pd(0)-catalyzed allylic alkylation is the ability to take reactants that are meso and desymmetrize them in the resulting products through the addition of a chiral ligand for the Pd metal. Draw the two h3 -allylic complexes formed in this reaction of the following reactant wit

Organic Chemistry 6
Suggest reagents and the other fragment that could be used to carry out the indicated conversion. B(OH)2 C4H9 N N N R N N N N R N HO Cl

Organic Chemistry 6
Show how the following compound could be prepared by a Suzuki reaction. NBn OBn OBn OMe BnO

Organic Chemistry 6
It is typically very diffi cult to do a substitution reaction on an aromatic ring when the leaving group is fl anked by two other bulky substituents. Moreover, in Section 22.3, we found that nucleophilic aromatic substitution requires strongly electron-withdrawing groups on the benzene ring. However,

Organic Chemistry 6
The compound eutypine is an antibacterial agent isolated from the fungus Eutypa lata. This fungus results in a disease common to vineyards called eutyposis. Give a sequence of reactions that will take the following reactant and give eutypine when the other reactants used in the sequence are acetylene

Organic Chemistry 6
When the Pd(0)-catalyzed reactions covered in this chapter are run with a slight pressure of carbon monoxide, it is often found that a ketone is created as the product. For example, the following Stille coupling conditions with added CO give the product shown. Write a mechanism for how this reaction

Organic Chemistry 6
Many of the cross-coupling reactions described in this chapter have been used to make fascinating polymeric materials, as are covered in Chapter 29. Give the proper reactants to create the following polymers and name the coupling reaction involved. C6H13 C6H13 n n

Organic Chemistry 6
b-Lactames are amides in four-membered rings and are common elements found in antibiotics. Show what reagents would be involved in creating the following series of b-lactames using a common vinyl trifl ate in each case. S CO2Bn N N H Ph O O S CO2Bn N N H Ph S CO2Bn N N H Ph O O O O S CO2Bn OEt N N H

Organic Chemistry 6
The creation of very large ring systems is often diffi cult and challenging. The following macrocyclic ring was created using one of the coupling reactions described in this chapter. Which one was used, and what was the starting material? HO OH O O O

Organic Chemistry 6
As presented in the chapter, the Sonogashira coupling reaction is commonly used to create diaryl alkynyl structures. However, it can also be used to create divinyl alkynyl structures. The following sequence of reactions creates such a product. Write possible reactants that would be placed in the boxe

Organic Chemistry 6
The cyclic ester (lactone) Exaltolide has a musk-like fragrance and is used as a fi xative in perfumery. Show how this compound could be synthesized from the indicated starting material. Give the structure of R. OR O O O O O Exaltolide

Organic Chemistry 6
Predict the product of each alkene metathesis reaction using a Ru-nucleophilic carbene catalyst. 5 mole % Ru catalyst CH2Cl2, 408C, 30 min 5 mole % Ru catalyst CH2Cl2, 408C, 30 min (a) (b) OAc OAc O O O

Organic Chemistry 6
The following transformation can be accomplished by reactions we have studied in this chapter and Chapter 20. Name the type of reaction used in each step. (1) (3) MeOOC MeOOC (2) MeOOC MeOOC MeOOC MeOOC ?

Organic Chemistry 6
Following is an outline of the stereospecific synthesis of the Corey lactone. Professor E. J. Corey (Harvard University) describes it in this way. The fi rst general synthetic route to all the known prostaglandins was developed by way of bicycloheptene intermediates. The design was guided by the requ

Organic Chemistry 6
Chapmans (O. L. Chapman, then at Iowa State, later UCLA) classic total synthesis of (6)-Carpanone is so remarkably simple that it is used as an undergraduate laboratory preparation. It is modeled on a possible biosynthetic route for this lignan-derived natural product. Phenol oxidations fi gure promi

Organic Chemistry 6
Gilvocarcin M is isolated from Streptomyces strains and has strong antitumor activity. O O OMe OMe OH OH OH OH H O CH3 H3C Gilvocarcin M Suzuki and coworkers were able to carry out the total synthesis of naturally occurring (2)-gilvocarcin M. Their synthesis included the following steps. (The wavy li

Organic Chemistry 6
Vancomycin is an important antibiotic. It is isolated from the bacterium Streptomyces orientalis and functions by inhibiting bacterial mucopeptide synthesis. It is a last line of defense against the resistant Staph organisms that are now common in hospitals. NH N H N H H N H N Vancomycin aglycon O H

Organic Chemistry 6
E. J. Coreys 1964 total synthesis of a-caryophyllene (essence of cloves) solves a number of problems of construction of unusual-sized rings. -Caryophyllene H H .The fi rst step uses an effi cient photochemical [2 1 2] reaction. The desired stereochemistry and regiochemistry had been predicted based o

Organic Chemistry 6
Over the past several decades, chemists have developed a number of synthetic methodologies for the synthesis of steroid hormones. One of these, developed by Lutz Tietze at the Institut fr Organische Chemie der Georg-August-Universitt, Gttingen, Germany, used a double Heck reaction to create ring B of