Chapter 23 Complete Test Bank Introduction To Organometallic

Organic Chemistry, 4e (Klein)

Chapter 23 Introduction to Organometallic Compounds

1) Which of the compounds shown has the most nucleophilic carbon atom?

A) CH3Cl

B) CH3Li

C) (CH3)2Zn

D) (CH3)2Cu

Diff: 1

Learning Objective: 23.1 Describe the structural features of organometallic compounds, and how this results in reactivity

2) Which of the compounds shown has the most nucleophilic carbon atom?

A) I

B) II

C) III

D) IV

Diff: 1

Learning Objective: 23.1 Describe the structural features of organometallic compounds, and how this results in reactivity

3) Which of the compounds shown has the least nucleophilic carbon atom?

A) CH3CH2MgBr

B) CH3CH2MgI

C) (CH3CH2)2Zn

D) (CH3CH2)2Cu

Diff: 2

Learning Objective: 23.1 Describe the structural features of organometallic compounds, and how this results in reactivity

4) Which of the compounds shown has the most ionic character in the C-M bond?

A) HC≡CMgBr

B) HC≡CK

C) HC≡CNa

D) HC≡CLi

Diff: 1

Learning Objective: 23.1 Describe the structural features of organometallic compounds, and how this results in reactivity

5) Which of the choices has the most polar bond?

A) C—B

B) C—Pd

C) C—Zn

D) C—Pt

Diff: 2

Learning Objective: 23.1 Describe the structural features of organometallic compounds, and how this results in reactivity

6) What functional group most typically results as a stable final product when a Grignard reagent reacts with an acid halide, after aqueous workup?

A) a primary alcohol

B) a secondary alcohol

C) a tertiary alcohol

D) a ketone

E) a nitrile

Diff: 2

Learning Objective: 23.1 Describe the structural features of organometallic compounds, and how this results in reactivity

7) What functional group typically results when an organocopper compound (lithium organocuprate) reacts with an acid chloride?

A) a primary alcohol

B) a secondary alcohol

C) a tertiary alcohol

D) a ketone

E) a nitrile

Diff: 2

Learning Objective: 23.1 Describe the structural features of organometallic compounds, and how this results in reactivity

8) Which of the given statements is false regarding the preparation of organolithium compounds?

A) Organolithium compounds can be made from alkyl halides (R-X).

B) Organolithium compounds can be made from aryl halides (Ar-X).

C) Vinyl halides cannot be used to form vinyl lithium reagents.

D) Lithium halides are byproducts of the reaction of lithium metal with alkyl halides.

E) It is necessary to use two equivalents of lithium metal.

Diff: 1

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

9) Why is ethanol not a viable solvent in the synthesis of Grignard reagents?

A) Ethanol will form hydrogen bonds, inhibiting the reaction.

B) The —OH proton is too acidic.

C) The —OH group is too unreactive.

D) Grignard reagents do not dissolve in ethanol.

E) The —OH proton is too basic.

Diff: 1

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

10) Explain why the solvent for a Grignard reaction must be free of water.

A) Water will form hydrogen bonds, inhibiting the reaction.

B) Water acts as a strong base in this context.

C) Water consumes the Grignard reagent.

D) Grignard reagents do not dissolve in water.

E) The reactant is more likely to react with water than with the Grignard reagent.

Diff: 1

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

11) Which of choices lists only good solvents that should be used in the preparation of organometallic reagents such as organolithiums and Grignard reagents?

A) ethanol, water, and diethyl ether

B) diethyl ether, tetrahydrofuran, and dioxane

C) cyclohexanol, tetrahydrofuran, and water

D) tetrahydrofuran, dioxane, and water

E) dioxane, benzene, and water

Diff: 2

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

12) Diethyl ether is a good solvent to be used with Grignard reagents. Which of the given explanations for this fact is false?

A) It has a very high boiling point, so it can be heated to drive the Grignard formation to completion.

B) It can serve as a Lewis base and stabilize the Grignard reagent, allowing time for the reaction to occur.

C) It is polar enough to stabilize the Grignard reagent.

D) It is aprotic and thus is not acidic enough to react with the Grignard reagent.

Diff: 2

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

13) Which alkyl halide is most reactive with magnesium metal?

A) CH3CH2CH2Br

B) CH3CH2CH2F

C) CH3CH2CH2I

D) CH3CH2CH2Cl

Diff: 1

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

14) Which alkyl halide is least reactive with magnesium metal?

A) CH3CH2CH2Br

B) CH3CH2CH2F

C) CH3CH2CH2I

D) CH3CH2CH2Cl

Diff: 1

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

15) Which of the given functional groups does not afford an alcohol when treated with a Grignard reagent followed by a protic work-up?

A) a ketone

B) an aldehyde

C) an ester

D) an epoxide

E) a nitrile

Diff: 2

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

16) What product is formed when formaldehyde reacts with one equivalent of a Grignard reagent?

A) a primary alcohol

B) a secondary alcohol

C) a tertiary alcohol

D) a carboxylic acid

E) a ketone

Diff: 1

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

17) What product is formed when butanal reacts with one equivalent of a Grignard reagent?

A) a primary alcohol

B) a secondary alcohol

C) a tertiary alcohol

D) a carboxylic acid

E) a ketone

Diff: 1

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

18) What product is formed when 2-pentanone reacts with one equivalent of a Grignard reagent?

A) a primary alcohol

B) a secondary alcohol

C) a tertiary alcohol

D) a carboxylic acid

E) a ketone

Diff: 1

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

19) What product is formed when ethylene oxide reacts with one equivalent of a Grignard reagent?

A) a primary alcohol

B) a secondary alcohol

C) a tertiary alcohol

D) a carboxylic acid

E) a ketone

Diff: 1

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

20) What product is formed when carbon dioxide reacts with one equivalent of a Grignard reagent?

A) a primary alcohol

B) a secondary alcohol

C) a tertiary alcohol

D) a carboxylic acid

E) a ketone

Diff: 1

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

21) What product is formed when an ester reacts with two equivalents of a Grignard reagent?

A) a primary alcohol

B) a secondary alcohol

C) a tertiary alcohol

D) a carboxylic acid

E) a ketone

Diff: 1

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

22) What product is formed when a nitrile reacts with one equivalent of a Grignard reagent?

A) a primary alcohol

B) a secondary alcohol

C) a tertiary alcohol

D) a carboxylic acid

E) a ketone

Diff: 1

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

23) What product is formed when a nitrile reacts with two equivalent of a Grignard reagents?

A) a primary alcohol

B) a secondary alcohol

C) a tertiary alcohol

D) a carboxylic acid

E) a ketone

Diff: 1

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

24) What is the product of the sequence shown?

A) I

B) II

C) III

D) IV

E) V

Diff: 2

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

25) What is the final product of the sequence shown?

A) I

B) II

C) III

D) IV

E) V

Diff: 2

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

26) What is the final product of the sequence shown?

A) I

B) II

C) III

D) IV

E) V

Diff: 2

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

27) What is the final product of the sequence shown?

A) I

B) II

C) III

D) IV

E) V

Diff: 2

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

28) What is the final product of the sequence shown?

A) I

B) II

C) III

D) IV

E) V

Diff: 2

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

29) What is the product of the sequence shown?

A) I

B) II

C) III

D) IV

E) V

Diff: 2

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

30) What is the final of the sequence shown?

A) I

B) II

C) III

D) IV

Diff: 3

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

31) What is the product of the sequence shown?

A) I

B) II

C) III

D) IV

E) none of the them

Diff: 3

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

32) What is the name of the product of the reaction sequence shown?

A) 3-methylbromobenzene

B) 4-methylbenzoic acid

C) p-bromobenzene

D) p-methyl toluene

E) 2-methylbenzoic acid

Diff: 3

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

33) What is the product of the sequence shown?

A) I

B) II

C) III

D) IV

E) V

Diff: 3

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

34) Which reactant would yield the product shown as the major isomeric product?

A) I

B) II

C) III

D) IV

E) none of the above

Diff: 2

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

35) What is the starting material indicated by question marks in the reaction below?

A) I

B) II

C) III

D) IV

E) The product cannot be formed directly from one of the reactants above.

Diff: 2

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

36) Starting from bromobenzene and any other reagents with two carbons or fewer, propose a synthesis of the compound shown.

A) 1. Mg, Et2O; 2. ethylene oxide; 3. H3O+; 4. PCC

B) 1. Mg, Et2O; 2. CH3OH; 3. H3O+; 4. PCC

C) 1. Mg, Et2O; 2. ethylene oxide; 3. PCC

D) 1. Mg, Et2O; 2. ethylene oxide; 3. H2SO4

E) 1. Mg, H2O; 2. ethylene oxide; 3. H3O+

Diff: 2

Learning Objective: 23.2 Discuss the preparation, properties, and reactivity of organolithium and organomagnesium compounds

37) Which of the given statements is(are) true regarding the preparation of Gilman reagents?

A) Gilman reagents can be made from alkyl halides (R-X).

B) Gilman reagents can be made from aryl halides (Ar-X).

C) Gilman reagents can be made from organolithium reagents.

D) Lithium halides are byproducts of the reaction to make Gilman reagents.

E) all of the above

Diff: 1

Learning Objective: 23.3 Describe the preparation of Gilman reagents and how they react

38) Which of the given reagents cannot be used in the synthesis of a Gilman reagent?

A) lithium metal

B) lithium halide

C) alkyl halide

D) aryl halide

E) vinyl halide

F) CuBr

Diff: 1

Learning Objective: 23.3 Describe the preparation of Gilman reagents and how they react

39) Which of the choices lists only electrophiles that are commonly used with Gilman reagents to form C-C bonds?

A) acid chlorides, α,β-unsaturated ketones, and alkyl halides

B) α,β-unsaturated ketones, esters, and amides

C) esters, amides, and alkyl halides

D) alkyl halides, acid chlorides, and amides

E) amides, acid chlorides, and esters

Diff: 1

Learning Objective: 23.3 Describe the preparation of Gilman reagents and how they react

40) Which of the given electrophiles are commonly used with Gilman reagents to form C-C bonds?

A) alkyl halides

B) aryl halides

C) vinyl halides

D) acyl halides

E) all the above

Diff: 1

Learning Objective: 23.3 Describe the preparation of Gilman reagents and how they react

41) Which of the given statements is false regarding the reactivity of Gilman reagents?

A) They react with acyl halides to give ketones.

B) They react with α,β-unsaturated ketones to give alcohols.

C) They react with alkyl halides or aryl halides in a coupling reaction.

D) They are unreactive with tertiary halides.

Diff: 1

Learning Objective: 23.3 Describe the preparation of Gilman reagents and how they react

42) The Corey-Posner/Whitesides-House reaction couples a lithium dialkyl cuprate with all but which of the given choices?

A) primary alkyl halides

B) tertiary alkyl halides

C) aryl halides

D) methyl halides

E) vinyl halides

Diff: 1

Learning Objective: 23.3 Describe the preparation of Gilman reagents and how they react

43) Which of the choices would react fastest in the Corey-Posner/Whitesides-House reaction?

A) cyclohexyl chloride

B) cyclohexyl iodide

C) tert-butyl chloride

D) tert-butyl iodide

Diff: 1

Learning Objective: 23.3 Describe the preparation of Gilman reagents and how they react

44) What is the product of the reaction shown?

A) (E)-1-phenyl-1-pentene

B) (Z)-1-phenyl-1-pentene

C) (E)-1-phenyl-2-pentene

D) (Z)-1-phenyl-2-pentene

E) 2-phenyl-1-pentene

Diff: 2

Learning Objective: 23.3 Describe the preparation of Gilman reagents and how they react

45) What is the best reagent for the reaction below?

A) I

B) II

C) III

D) IV

Diff: 2

Learning Objective: 23.3 Describe the preparation of Gilman reagents and how they react

46) Which of the given Gilman reagents could be used with a vinyl halide to afford the (E,E)-diene shown below? Select all that apply.

A) I

B) II

C) III

D) IV

E) II and III

Diff: 2

Learning Objective: 23.3 Describe the preparation of Gilman reagents and how they react

47) Gillman reagents are intolerant to the presence of what functional group?

A) ketone

B) ester

C) amide

D) All of the functional groups above are not compatible with Gilman reagents.

Diff: 1

Learning Objective: 23.3 Describe the preparation of Gilman reagents and how they react

48) Starting from bromobenzene and ________ as the only source of carbon atoms, 1-phenylcyclohexene can be synthesized using a Corey-Posner/Whitesides-House coupling reaction.

A) 1-iodocyclohexene

B) 3-iodocyclohexene

C) iodocyclohexane

D) (iodomethyl)cyclohexane

Diff: 2

Learning Objective: 23.3 Describe the preparation of Gilman reagents and how they react

49) Starting from vinyl chloride and ________ as the only source of carbon atoms, 1-heptene can be synthesized using a Corey-Posner/Whitesides-House coupling reaction.

A) 1-bromopropane

B) 2-bromopentane

C) 1-bromohexane

D) 1-bromopentane

Diff: 2

Learning Objective: 23.3 Describe the preparation of Gilman reagents and how they react

50) A total synthesis of ingenol utilized the Corey-Posner/Whitesides-House coupling reaction in a key C-C bond forming step (J. Am. Chem. Soc. 2002, 124, 9726). What reagent would be most appropriate to perform this transformation?

A) CH3MgBr

B) CH3CH2OH

C) HOMgBr

D) (CH3)2CuLi

E) CH3CuLi

Diff: 2

Learning Objective: 23.3 Describe the preparation of Gilman reagents and how they react

51) What is the product of the reaction shown?

A) I

B) II

C) III

D) IV

E) V

Diff: 2

Learning Objective: 23.3 Describe the preparation of Gilman reagents and how they react

52) The synthesis shown is not likely to work. Which of the given explanations is correct?

A) Lithium cannot react with aryl halides to form organolithium compounds.

B) CH3CH2Br does not do cross coupling in Corey-Posner/Whitesides-House reactions.

C) The cuprate formed would react with the ketone.

D) The organolithium formed would react with the ketone.

Diff: 2

Learning Objective: 23.3 Describe the preparation of Gilman reagents and how they react

53) Which of the choices is a Simmons-Smith cyclopropanation?

A) R-X + Zn →

B) R2C=CR2 + CH2I2 + Zn-Cu →

C) CHCl3 + NaOH →

D) R2C=CHI + (CH3)2CuLi →

Diff: 1

Learning Objective: 23.4 Discuss the Simmons-Smith cyclopropanation reaction and the carbenoid reagent

54) The Simmons-Smith reaction involves the formation of ________.

A) alkenes

B) alkynes

C) cyclopropanes

D) cuprates

Diff: 1

Learning Objective: 23.4 Discuss the Simmons-Smith cyclopropanation reaction and the carbenoid reagent

55) What are the conditions for the reaction shown?

A) CH2I2

B) 1. MgEt2O; 2. Bu3/SnCl

C) CH2I2 / Zn-Cu

D) Mg/EtO

E) 9-BBN

Diff: 2

Learning Objective: 23.4 Discuss the Simmons-Smith cyclopropanation reaction and the carbenoid reagent

56) What is the predicted product of reaction shown?

A) I

B) II

C) III

D) IV

Diff: 2

Learning Objective: 23.4 Discuss the Simmons-Smith cyclopropanation reaction and the carbenoid reagent

57) What are the product(s) of the reaction shown? Select all that apply.

A) I

B) II

C) III

D) IV

Diff: 2

Learning Objective: 23.4 Discuss the Simmons-Smith cyclopropanation reaction and the carbenoid reagent

58) What are the product(s) of the reaction shown?

A) I and II

B) II and III

C) I and IV

D) II and IV

E) I and III

Diff: 2

Learning Objective: 23.4 Discuss the Simmons-Smith cyclopropanation reaction and the carbenoid reagent

59) What are the product(s) of the reaction shown?

A) I and II

B) II and III

C) III and IV

D) I and IV

E) II and IV

Diff: 2

Learning Objective: 23.4 Discuss the Simmons-Smith cyclopropanation reaction and the carbenoid reagent

60) Which of the given statements is false?

A) Carbenes are generally long lived.

B) Carbenes have a carbon with non-bonding electrons.

C) Carbenes have a carbon missing an octet.

D) Carbenes can be formed by α-elimination.

E) Carbenes are electrophilic.

Diff: 1

Learning Objective: 23.4 Discuss the Simmons-Smith cyclopropanation reaction and the carbenoid reagent

61) Treatment of chloroform (CHCl3) with strong bases results in ________, which is mechanistically described as a ________.

A) α-elimination; loss of leaving group followed by deprotonation.

B) α-elimination; deprotonation followed by a loss of leaving group.

C) β-elimination; deprotonation followed by loss of leaving group.

D) β-elimination; concerted deprotonation and loss of leaving group.

Diff: 2

Learning Objective: 23.4 Discuss the Simmons-Smith cyclopropanation reaction and the carbenoid reagent

62) A total synthesis of ingenol utilized a dibromocyclopropanation via a carbene intermediate (J. Am. Chem. Soc. 2002, 124, 9726). What key type of reagent is missing from the reaction conditions?

A) Bronsted Acid

B) Bronsted Base

C) radical initiator

D) Lewis Acid catalyst

Diff: 2

Learning Objective: 23.4 Discuss the Simmons-Smith cyclopropanation reaction and the carbenoid reagent

63) The reaction of a carbene with an alkene to make a cyclopropane commonly goes through which type of mechanism?

A) proton transfer

B) loss of leaving group

C) cycloaddition

D) α-elimination

Diff: 1

Learning Objective: 23.4 Discuss the Simmons-Smith cyclopropanation reaction and the carbenoid reagent

64) What are the predicted products of the reaction shown?

A) I

B) II

C) III

D) IV

E) V

Diff: 2

Learning Objective: 23.4 Discuss the Simmons-Smith cyclopropanation reaction and the carbenoid reagent

65) What are the predicted products of the reaction shown?

A) I

B) II

C) III

D) IV

E) V

Diff: 2

Learning Objective: 23.4 Discuss the Simmons-Smith cyclopropanation reaction and the carbenoid reagent

66) A report on the synthesis of Aromatic Erythrina Alkaloids uses the given transformation (Org. Lett. 2006, 8, 2143). What are reaction conditions?

A) CHCl3, t-BuOK

B) CH2I2

C) CH2I2 / Zn-Cu

D) Mg/EtO

E) 9-BBN

Diff: 3

Learning Objective: 23.4 Discuss the Simmons-Smith cyclopropanation reaction and the carbenoid reagent

67) Elaboration of an advanced intermediate toward the synthesis of the pulmoside aglycon is shown below. What are the structures of intermediates A-C? (J. Am. Chem. Soc. 2013, 135, 2501.)

A) I is A, II is B, and III is C

B) I is A, II is C, and III is B

C) II is A, I is B, and III ic C

D) III is A, II is B, and I is C

E) I is A, IV is B, and III is C

Diff: 3

Learning Objective: 23.4 Discuss the Simmons-Smith cyclopropanation reaction and the carbenoid reagent

68) The Stille reaction involves coupling of which pair of reagents?

A) organohalide and organotin

B) organohalide and organoboron

C) organotin and organozinc

D) organoboron and organozinc

Diff: 1

Learning Objective: 23.5 Describe the Stille coupling, the three stages involved in the mechanism, and chemistry of palladium and organostannanes

69) Which catalysts are common in the Stille coupling reaction?

A) Pd(PPh3)4

B) Pd (OAc)2

C) PdCl2(PPh3)2

D) All of the above

Diff: 1

Learning Objective: 23.5 Describe the Stille coupling, the three stages involved in the mechanism, and chemistry of palladium and organostannanes

70) The Stille reaction couples organotin reagents with all but one of the choices listed. Which of the choices is not a common coupling partner?

A) —I

B) —Br

C) —Cl

D) —F

E) —OTf

Diff: 1

Learning Objective: 23.5 Describe the Stille coupling, the three stages involved in the mechanism, and chemistry of palladium and organostannanes

71) Which of the choices is not a mechanistic step in the generally accepted mechanism of the Stille coupling?

A) transmetallation

B) reductive elimination

C) syn-elimination

D) oxidative addition

Diff: 1

Learning Objective: 23.5 Describe the Stille coupling, the three stages involved in the mechanism, and chemistry of palladium and organostannanes

72) Which of the given R groups (R-SnBu3) would undergo the slowest transmetallation in a Stille coupling reaction?

A) alkyl

B) aryl

C) vinyl

D) benzyl

Diff: 1

Learning Objective: 23.5 Describe the Stille coupling, the three stages involved in the mechanism, and chemistry of palladium and organostannanes

73) Which of the given R groups (R-SnBu3) would undergo the fastest transmetallation in a Stille coupling reaction?

A) alkyl

B) aryl

C) vinyl

D) benzyl

Diff: 1

Learning Objective: 23.5 Describe the Stille coupling, the three stages involved in the mechanism, and chemistry of palladium and organostannanes

74) What is the predicted product of the reaction shown?

A) I

B) II

C) III

D) IV

Diff: 3

Learning Objective: 23.5 Describe the Stille coupling, the three stages involved in the mechanism, and chemistry of palladium and organostannanes

75) In a total synthesis of the bisnortriterpenoid rubriflordilactone A, a key step involved the given transformation. Draw the product. (J. Am. Chem. Soc. 2014, 136, 16477).

A) I

B) II

C) III

D) IV

E) V

Diff: 3

Learning Objective: 23.5 Describe the Stille coupling, the three stages involved in the mechanism, and chemistry of palladium and organostannanes

76) What is the predicted product of the reaction shown?

A) (2E,4Z)-4-methylhepta-2,4-diene

B) (2Z,4E)-4-methylhepta-2,4-diene

C) (3E,5Z)-4-methylhepta-3,5-diene

D) (3Z,5Z)-4-methylhepta-3,5-diene

E) (3E,5E)-4-methylhepta-3,5-diene

Diff: 3

Learning Objective: 23.5 Describe the Stille coupling, the three stages involved in the mechanism, and chemistry of palladium and organostannanes

77) Biselyngbyolide A is a cytotoxic natural product that shows promise for the treatment of bone lytic diseases. Shown below is a recent synthesis of this molecule (Org. Lett. 2014, 16, 2858). Give the structure of intermediate 1 and Biselyngbyolide A. Hint: PPTS is a strong organic acid.

A) Intermediate 1 is I and Biselyngbyolide A is II.

B) Intermediate 1 is II and Biselyngbyolide A is III.

C) Intermediate 1 is I and Biselyngbyolide A is II.

D) Intermediate 1 is II and Biselyngbyolide A is I.

E) Intermediate 1 is III and Biselyngbyolide A is II.

Diff: 3

Learning Objective: 23.5 Describe the Stille coupling, the three stages involved in the mechanism, and chemistry of palladium and organostannanes

78) What is the product of the reaction shown?

A) I

B) II

C) III

D) IV

Diff: 1

Learning Objective: 23.5 Describe the Stille coupling, the three stages involved in the mechanism, and chemistry of palladium and organostannanes

79) Which of the choices is a boronic ester?

A) I

B) II

C) III

D) IV

Diff: 1

Learning Objective: 23.6 Describe the Suzuki coupling, its mechanism, and chemistry of organoboron compounds

80) Which of the choices is a boronic acid?

A) I

B) II

C) III

D) IV

Diff: 2

Learning Objective: 23.6 Describe the Suzuki coupling, its mechanism, and chemistry of organoboron compounds

81) Which of the indicated bonds could be formed by a Suzuki coupling but not a Stille coupling?

A) a-b

B) c-d

C) d-e

D) f-g

Diff: 3

Learning Objective: 23.6 Describe the Suzuki coupling, its mechanism, and chemistry of organoboron compounds

82) What is the product of the reaction shown?

A) I

B) II

C) III

D) IV

Diff: 2

Learning Objective: 23.6 Describe the Suzuki coupling, its mechanism, and chemistry of organoboron compounds

83) Which of the given choices are advantages of the Suzuki coupling over the Stille coupling? Select all that apply.

A) Organoboron compounds are less expensive than organotin compounds.

B) Organoboron compounds are less toxic than organotin compounds.

C) Formation of alkyl-aryl bonds is possible.

D) The reaction requires a base.

Diff: 2

Learning Objective: 23.6 Describe the Suzuki coupling, its mechanism, and chemistry of organoboron compounds

84) What is the product of the reaction sequence shown?

A) I

B) II

C) III

D) IV

Diff: 3

Learning Objective: 23.6 Describe the Suzuki coupling, its mechanism, and chemistry of organoboron compounds

85) Macrocyle A was formed by a two- step process involving a hydroboration of an alkene in B followed by an intramolecular Suzuki coupling of a vinyl iodide in B to form the indicated bond below. What is the structure of B? (Org. Lett. 2002, 4, 2205).

A) I

B) II

C) III

D) IV

E) V

Diff: 3

Learning Objective: 23.6 Describe the Suzuki coupling, its mechanism, and chemistry of organoboron compounds

86) Which two reagents can be coupled in a Suzuki reaction to form the product shown?

Diff: 3

Learning Objective: 23.6 Describe the Suzuki coupling, its mechanism, and chemistry of organoboron compounds

87) Which of the organometallic species shown is not associated with the Negishi coupling reaction?

A) organozinc

B) organoaluminium

C) organoboron

D) organozirconium

Diff: 1

Learning Objective: 23.7 Describe the Negishi coupling, its mechanism, and chemistry of organozinc compounds and their precursors

88) Which of the organozinc compounds shown can be used in a Negishi coupling reaction?

A) a vinyl organozinc

B) an alkyl organozinc

C) an aryl organozinc

D) a benzyl organozinc

E) all of the above

Diff: 1

Learning Objective: 23.7 Describe the Negishi coupling, its mechanism, and chemistry of organozinc compounds and their precursors

89) The reaction shown is an example of the ________.

A) Stille coupling

B) Suzuki coupling

C) Negishi coupling

D) Heck reaction

Diff: 1

Learning Objective: 23.7 Describe the Negishi coupling, its mechanism, and chemistry of organozinc compounds and their precursors

90) Which of the given methods is not a common/useful way to make an organozinc reagent?

A) alkyl halide + Zn in ether

B) alkyl halide + Mg followed by ZnBr2

C) organolithium +ZnBr2

D) organoborane + Zn

Diff: 1

Learning Objective: 23.7 Describe the Negishi coupling, its mechanism, and chemistry of organozinc compounds and their precursors

91) A synthesis of the taxadienone system involves the reaction shown (Org. Process. Res. Dev. 2015, 19, 284). What is the product?

A) I

B) II

C) III

D) IV

Diff: 2

Learning Objective: 23.7 Describe the Negishi coupling, its mechanism, and chemistry of organozinc compounds and their precursors

92) What is the major product of the following reaction?

A) I

B) II

C) III

D) IV

Diff: 2

Learning Objective: 23.7 Describe the Negishi coupling, its mechanism, and chemistry of organozinc compounds and their precursors

93) The final steps of Sammakia's total synthesis of caerulomycin C involved the reaction below (Org. Lett. 2002, 4, 2385). What is the structure of the product?

A) I

B) II

C) III

D) IV

E) V

Diff: 2

Learning Objective: 23.7 Describe the Negishi coupling, its mechanism, and chemistry of organozinc compounds and their precursors

94) Which statement is true of the Heck reaction?

A) Pd should not be used.

B) It requires the presence of ethanol.

C) It requires the presence of a base.

D) It is not a coupling reaction.

E) It requires an alkane reactant.

Diff: 1

Learning Objective: 23.8 Describe the Heck reaction and its mechanism

95) Which of the alkenes shown is the most reactive in the Heck reaction?

A) I

B) II

C) III

D) IV

Diff: 2

Learning Objective: 23.8 Describe the Heck reaction and its mechanism

96) Which of the alkenes shown is the most reactive in the Heck reaction?

A) I

B) II

C) III

D) IV

Diff: 2

Learning Objective: 23.8 Describe the Heck reaction and its mechanism

97) Which of the dienes shown could not be formed as the major organic product in a Heck reaction with methyl vinyl ketone as the reactant alkene?

A) I

B) II

C) III

D) IV

Diff: 2

Learning Objective: 23.8 Describe the Heck reaction and its mechanism

98) Which of the choices is not a step in the Heck reaction catalytic cycle?

A) transmetallation

B) reductive elimination

C) syn-elimination

D) oxidative addition

E) syn-addition

Diff: 1

Learning Objective: 23.8 Describe the Heck reaction and its mechanism

99) What is the major product for the Heck reaction shown?

A) I

B) II

C) III

D) IV

Diff: 2

Learning Objective: 23.8 Describe the Heck reaction and its mechanism

100) What is the major product for the reaction shown?

A) I

B) II

C) III

D) IV

Diff: 2

Learning Objective: 23.8 Describe the Heck reaction and its mechanism

101) Which alkene would be used in the Heck reaction below?

A) I

B) II

C) III

D) IV

Diff: 2

Learning Objective: 23.8 Describe the Heck reaction and its mechanism

102) Which of the choices shown are possible Heck reaction products?

A) I

B) II

C) III

D) all of the above

Diff: 3

Learning Objective: 23.8 Describe the Heck reaction and its mechanism

103) Which statement is true of the reaction shown?

A) Compound I is the major product because it involves an intermolecular reaction.

B) Compound II is the major product and is formed the most easily.

C) Compound III is the major product.

D) Compounds I and II are equally likely to be formed, but compound III is not formed.

E) Compounds II and III are equally likely to be formed, but compound I is not formed.

Diff: 3

Learning Objective: 23.8 Describe the Heck reaction and its mechanism

104) Heck reactions with allylic alcohols have a tendency to form carbonyl products. Considering the mechanism for the Heck reaction, how would the ketone product shown form?

A) Syn elimination would yield an enol that then tautomerizes to a ketone.

B) Syn elimination would yield a ketone directly.

C) Tautomerization would occur first.

D) Anti elimination would yield a ketone directly.

E) Anti elimination would yield a ketone after several steps.

Diff: 2

Learning Objective: 23.8 Describe the Heck reaction and its mechanism

105) What coupling partners can be used to prepare the given compound in a Heck reaction?

A) Cyclohexene and p-bromobenzaldehyde

B) Toluene and 2-bromocyclohexene

C) Toluene and bromocyclohexane

D) Cyclohexene and m-bromobenzaldehyde

E) Cyclohexene and o-bromobenzaldehyde

Diff: 2

Learning Objective: 23.8 Describe the Heck reaction and its mechanism

106) What coupling partners can be used to prepare the given compound in a Heck reaction?

A) ethyl vinyl ketone and p-methylstyrene

B) ethyl vinyl ketone and 4-iodotoluene

C) p-methylstyrene and propionoyl chloride

D) (E)-1-(2-bromovinyl)-4-methylbenzene and propionoyl chloride

Diff: 2

Learning Objective: 23.8 Describe the Heck reaction and its mechanism

107) What coupling partners can be used to prepare the given compound in a Heck reaction?

A) p-nitrostyrene and (E)-(2-bromovinyl)benzene

B) p-nitrostyrene and (Z)-(2-bromovinyl)benzene

C) (E)-1-(2-bromovinyl)-4-nitrobenzene and styrene

D) (Z)-1-(2-bromovinyl)-4-nitrobenzene and styrene

Diff: 2

Learning Objective: 23.8 Describe the Heck reaction and its mechanism

108) Which of the choices can be used to make a C-C double bond?

A) Simmons-Smith reaction

B) Suzuki coupling

C) Negishi coupling

D) alkene metathesis

Diff: 1

Learning Objective: 23.9 Describe alkene metathesis, its mechanism, and applications

109) Which of the metathesis reactions shown would not form ethylene gas?

A) I

B) II

C) III

D) IV

Diff: 2

Learning Objective: 23.9 Describe alkene metathesis, its mechanism, and applications

110) Each intermediate in alkene metathesis is formed by ________ cycloaddition

A) [1 + 1]

B) [1 + 2]

C) [2 + 2]

D) [2 + 3]

E) [3 + 3]

Diff: 1

Learning Objective: 23.9 Describe alkene metathesis, its mechanism, and applications

111) Which of the choices is false regarding ring-opening metathesis?

A) Cyclic alkenes react to form dienes.

B) The Grubbs catalyst is commonly used.

C) Ethylene is typically formed in the reaction.

D) Ring opening metathesis can be performed in the presence of a variety of functional groups.

Diff: 1

Learning Objective: 23.9 Describe alkene metathesis, its mechanism, and applications

112) What is major the product for the reaction shown?

A) I

B) II

C) III

D) IV

E) V

Diff: 3

Learning Objective: 23.9 Describe alkene metathesis, its mechanism, and applications

113) Which of the choices are products of the given reaction?

A) I and II only

B) I and III only

C) II and III only

D) I, II, and III only

E) II, III, and IV only

Diff: 2

Learning Objective: 23.9 Describe alkene metathesis, its mechanism, and applications

114) In the given synthesis of a potent anti-cancer natural product, lasiodiplodin, which of the organometallic reactions shown are utilized? (J.Org. Chem. 2000, 65, 7990).

A) Suzuki Coupling only

B) Stille Coupling and ring-closing metathesis

C) Heck reaction and ring-closing metathesis

D) Heck reaction only

E) ring-opening metathesis only

Diff: 2

Learning Objective: 23.9 Describe alkene metathesis, its mechanism, and applications

115) What is the product of treating styrene with the Grubbs Catalyst?

A) E-stilbene only

B) Z-stilbene only

C) a mixture of E and Z stilbene

D) no reaction because the alkene is terminal

Diff: 1

Learning Objective: 23.9 Describe alkene metathesis, its mechanism, and applications

116) What diene is the reactant in the ring-closing metathesis reaction shown?

A) I

B) II

C) III

D) I or II

E) II or III

Diff: 2

Learning Objective: 23.9 Describe alkene metathesis, its mechanism, and applications

117) What is the predicted major product of the reaction shown?

A) I

B) II

C) III

D) IV

Diff: 3

Learning Objective: 23.9 Describe alkene metathesis, its mechanism, and applications

118) What is the product of the given ring-opening/ring-closing metathesis reaction? (J. Am. Chem. Soc. 1996, 118, 6634.)

A) I

B) II

C) III

D) IV

E) V

Diff: 3

Learning Objective: 23.9 Describe alkene metathesis, its mechanism, and applications

119) What is the product of the given ring-closing metathesis reaction?

A) I

B) II

C) III

D) IV

Diff: 3

Learning Objective: 23.9 Describe alkene metathesis, its mechanism, and applications

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