Chapter 26, Problem 26.32P

Draw the products formed in each reaction.

a. f.

b. g.

c. h. $\text{The product in }\left(\text{a}\right)\stackrel{{\left({\text{CH}}_{\text{3}}\right)}_{\text{2}}\text{CuLi}}{\to }$

d. i.

e. j.

Interpretation Introduction

(a)

Interpretation: The product formed in the given reaction is to be drawn.

Concept introduction: The treatment of $\text{KOC}{\left({\text{CH}}_{\text{3}}\right)}_{\text{3}}$ with ${\text{CHX}}_{\text{3}}$, yields a dihalocarbene that is ${\text{:CX}}_{\text{2}}$. This dihalocarbene is an electrophile that readily reacts with $\text{C}=\text{C}$ of an alkene to afford cyclopropane ring. This step leads to the formation of two new $\text{C}-\text{C}$ bonds.

Answer to Problem 26.32P

The product of the given reaction is,

Explanation of Solution

The given reaction involves treatment of an alkene with $\text{[1]}{\text{CHBr}}_{\text{3}}\text{,}\text{KOC}{\left({\text{CH}}_{\text{3}}\right)}_{\text{3}}$ followed by ${\left({\text{CH}}_{\text{3}}\right)}_{\text{2}}\text{CuLi}$.

The treatment of $\text{KOC}{\left({\text{CH}}_{\text{3}}\right)}_{\text{3}}$ with ${\text{CHBr}}_{\text{3}}$, yields a dihalocarbene that is ${\text{:CBr}}_{\text{2}}$. This dihalocarbene is an electrophile that readily reacts with $\text{C}=\text{C}$ of given alkene to afford dihalocyclopropane ring. This step leads to the formation of two new $\text{C}-\text{C}$ bonds. The dihalocyclopropane ring is converted to corresponding dimethyl cyclopropane by the treatment of given organocuprate reagent that is ${\left({\text{CH}}_{\text{3}}\right)}_{\text{2}}\text{CuLi}$.

The corresponding reaction is shown below.

Figure 1

Thus, the product of the given reaction is,

Figure 2

Conclusion

The product of the given reaction is drawn in Figure 2.

Interpretation Introduction

(b)

Interpretation: The product formed in the given reaction is to be drawn.

Concept introduction: The treatment of an organic halide with an alkene in the presence of $\text{Pd}$ catalyst to form an alkene that is highly substituted with a new $\text{C}-\text{C}$ bond is known as Heck reaction. Generally $\left[\text{Pd}{\left(\text{OAc}\right)}_2\right]$ in the presence of $\left[\text{P}{\left(o\text{-tolyl}\right)}_3\right]$ is utilized as catalyst. The reaction is carried out in the presence of organic base, like ${\text{Et}}_{\text{3}}\text{N}$.

Answer to Problem 26.32P

The product of the given reaction is,

Explanation of Solution

The given reaction involves treatment of an organic halide with an alkene in the presence of $\left[\text{Pd}{\left(\text{OAc}\right)}_2\right],\left[\text{P}{\left(o\text{-tolyl}\right)}_3\right]$, and base ${\text{Et}}_{\text{3}}\text{N}$.

The treatment of an organic halide with an alkene in the presence of $\text{Pd}$ catalyst to form an alkene that is highly substituted with a new $\text{C}-\text{C}$ bond is known as Heck reaction. Generally $\left[\text{Pd}{\left(\text{OAc}\right)}_2\right]$ in the presence of $\left[\text{P}{\left(o\text{-tolyl}\right)}_3\right]$ is utilized as catalyst. The reaction is carried out in the presence of organic base, like ${\text{Et}}_{\text{3}}\text{N}$.

The corresponding reaction is shown below.

Figure 3

Thus, the product of the given reaction is,

Figure 4

Conclusion

The product of the given reaction is drawn in Figure 4.

Interpretation Introduction

(c)

Interpretation: The product formed in the given reaction is to be drawn.

Concept introduction: The treatment of an organic halide with an alkene in the presence of $\text{Pd}$ catalyst to form an alkene that is highly substituted with a new $\text{C}-\text{C}$ bond is known as Heck reaction. Generally $\left[\text{Pd}{\left(\text{OAc}\right)}_2\right]$ in the presence of $\left[\text{P}{\left(o\text{-tolyl}\right)}_3\right]$ is utilized as catalyst. The reaction is carried out in the presence of organic base, like ${\text{Et}}_{\text{3}}\text{N}$.

Answer to Problem 26.32P

The product of the given reaction is,

Explanation of Solution

The given reaction involves treatment of an organic halide with an alkene in the presence of $\left[\text{Pd}{\left(\text{OAc}\right)}_2\right],\left[\text{P}{\left(o\text{-tolyl}\right)}_3\right]$, and base ${\text{Et}}_{\text{3}}\text{N}$.

The treatment of an organic halide with an alkene in the presence of $\text{Pd}$ catalyst to form an alkene that is highly substituted with a new $\text{C}-\text{C}$ bond is known as Heck reaction. Generally $\left[\text{Pd}{\left(\text{OAc}\right)}_2\right]$ in the presence of $\left[\text{P}{\left(o\text{-tolyl}\right)}_3\right]$ is utilized as catalyst. The reaction is carried out in the presence of organic base, like ${\text{Et}}_{\text{3}}\text{N}$.

The corresponding reaction is shown below.

Figure 5

Thus, the product of the given reaction is,

Figure 6

Conclusion

The product of the given reaction is drawn in Figure 6.

Interpretation Introduction

(d)

Interpretation: The product formed in the given reaction is to be drawn.

Concept introduction: The treatment of an organic halide $\left({\text{R}}^{\text{'}}\text{X}\right)$ with an organoborane reagent $\left({\text{RBY}}_{\text{2}}\right)$ in the presence of $\text{Pd}$ catalyst to afford the $\text{C}-\text{C}$ coupling is known as Suzuki reaction. During reaction, the metal catalyst is coordinated with some ligands, like ${\text{PPh}}_{\text{3}}$. The reaction is facilitated in the presence of strong inorganic base like ${\text{NaOCH}}_{\text{2}}{\text{CH}}_{\text{3}}$ or $\text{NaOH}$.

Answer to Problem 26.32P

The product of the given reaction is,

Explanation of Solution

The given reaction involves treatment of an organic halide with an organoborane reagent in the presence of $\text{Pd}{\left({\text{PPh}}_{\text{3}}\right)}_{\text{4}}$ and $\text{NaOH}$.

The treatment of an organic halide $\left({\text{R}}^{\text{'}}\text{X}\right)$ with an organoborane reagent $\left({\text{RBY}}_{\text{2}}\right)$ in the presence of $\text{Pd}$ catalyst to afford the $\text{C}-\text{C}$ coupling is known as Suzuki reaction. During reaction, the metal catalyst is coordinated with some ligands, like ${\text{PPh}}_{\text{3}}$. The reaction is facilitated in the presence of strong inorganic base like ${\text{NaOCH}}_{\text{2}}{\text{CH}}_{\text{3}}$ or $\text{NaOH}$.

The corresponding reaction is shown below.

Figure 7

Thus, the product of the given reaction is,

Figure 8

Conclusion

The product of the given reaction is drawn in Figure 8.

Interpretation Introduction

(e)

Interpretation: The product formed in the given reaction is to be drawn.

Concept introduction: The treatment of an organic halide $\left({\text{R}}^{\text{'}}\text{X}\right)$ with an organoborane reagent $\left({\text{RBY}}_{\text{2}}\right)$ in the presence of $\text{Pd}$ catalyst to afford the $\text{C}-\text{C}$ coupling is known as Suzuki reaction. During reaction, the metal catalyst is coordinated with some ligands, like ${\text{PPh}}_{\text{3}}$. The reaction is facilitated in the presence of strong inorganic base like ${\text{NaOCH}}_{\text{2}}{\text{CH}}_{\text{3}}$ or $\text{NaOH}$.

Answer to Problem 26.32P

The product of the given reaction is,

Explanation of Solution

The given reaction involves treatment of an organic halide with an organoborane reagent in the presence of $\text{Pd}{\left({\text{PPh}}_{\text{3}}\right)}_{\text{4}}$ and $\text{NaOH}$.

The treatment of an organic halide $\left({\text{R}}^{\text{'}}\text{X}\right)$ with an organoborane reagent $\left({\text{RBY}}_{\text{2}}\right)$ in the presence of $\text{Pd}$ catalyst to afford the $\text{C}-\text{C}$ coupling is known as Suzuki reaction. During reaction, the metal catalyst is coordinated with some ligands, like ${\text{PPh}}_{\text{3}}$. The reaction is facilitated in the presence of strong inorganic base like ${\text{NaOCH}}_{\text{2}}{\text{CH}}_{\text{3}}$ or $\text{NaOH}$.

The corresponding reaction is shown below.

Figure 9

Thus, the product of the given reaction is,

Figure 10

Conclusion

The product of the given reaction is drawn in Figure 10.

Interpretation Introduction

(f)

Interpretation: The product formed in the given reaction is to be drawn.

Concept introduction: The ring-closing metathesis (RCM) by Grubbs catalyst occurs, when the starting material is diene. This reaction is facilitated under high-dilution condition as it favors intramolecular metathesis instead of intermolecular metathesis.

Answer to Problem 26.32P

The product of the given reaction is,

Explanation of Solution

The given reaction involves treatment of a diene with Grubbs catalyst.

The ring-closing metathesis (RCM) by Grubbs catalyst occurs, when the starting material is diene. This reaction is facilitated under high-dilution condition as it favors intramolecular metathesis instead of intermolecular metathesis.

The corresponding reaction is shown below.

Figure 11

Thus, the product of the given reaction is,

Figure 12

Conclusion

The product of the given reaction is drawn in Figure 12.

Interpretation Introduction

(g)

Interpretation: The product formed in the given reaction is to be drawn.

Concept introduction: The nonhalogenated cyclopropanes are synthesized by the treatment of an alkene with ${\text{CH}}_{\text{2}}{\text{I}}_{\text{2}}$, in the presence of zinc-copper couple $\left[\text{Zn}\left(\text{Cu}\right)\right]$. This reaction is known as Simmons-Smith reaction.

Answer to Problem 26.32P

The product of the given reaction is,

Explanation of Solution

The given reaction involves treatment of an alkene with ${\text{CH}}_{\text{2}}{\text{I}}_{\text{2}}$, in the presence of zinc-copper couple $\left[\text{Zn}\left(\text{Cu}\right)\right]$.

The nonhalogenated cyclopropanes are synthesized by the treatment of an alkene with ${\text{CH}}_{\text{2}}{\text{I}}_{\text{2}}$, in the presence of zinc-copper couple $\left[\text{Zn}\left(\text{Cu}\right)\right]$. This reaction is known as Simmons-Smith reaction.

The corresponding reaction is shown below.

Figure 13

Thus, the product of the given reaction is,

Figure 14

Conclusion

The product of the given reaction is drawn in Figure 14.

Interpretation Introduction

(h)

Interpretation: The product formed in the given reaction is to be drawn.

Concept introduction: The treatment of $\text{KOC}{\left({\text{CH}}_{\text{3}}\right)}_{\text{3}}$ with ${\text{CHX}}_{\text{3}}$, yields a dihalocarbene that is ${\text{:CX}}_{\text{2}}$. This dihalocarbene is an electrophile that readily reacts with $\text{C}=\text{C}$ of an alkene to afford cyclopropane ring. This step leads to the formation of two new $\text{C}-\text{C}$ bonds.

Answer to Problem 26.32P

The product of the given reaction is,

Explanation of Solution

The given reaction involves treatment of product formed in part (a) with ${\left({\text{CH}}_{\text{3}}\right)}_{\text{2}}\text{CuLi}$.

The dihalocyclopropane ring is converted to corresponding bromomethylcyclopropane by the treatment of given organocuprate reagent that is ${\left({\text{CH}}_{\text{3}}\right)}_{\text{2}}\text{CuLi}$.

The corresponding reaction is shown below.

Figure 15

Thus, the product of the given reaction is,

Figure 16

Conclusion

The product of the given reaction is drawn in Figure 16.

Interpretation Introduction

(i)

Interpretation: The product formed in the given reaction is to be drawn.

Concept introduction: The treatment of an organic halide with $\text{Li}$$\left(\text{2}\text{equiv}\right)$ leads to the formation of an alkyl lithium. When alkyl lithium is further treated with $\text{CuI}$$\left(\text{0}\text{.5}\text{equiv}\right)$, it leads to the formation of organocuprate reagent. The formed organocuprate reagent reacts with another organic halide to form the coupling product (new $\text{C}-\text{C}$ bond).

Answer to Problem 26.32P

The product of the given reaction is,

Explanation of Solution

The given reaction involves treatment of chlorobutane with $\text{Li}$, followed by $\text{CuI}$ and an organic halide, which contains $\text{C}=\text{C}$.

The treatment of an organic halide with $\text{Li}$$\left(\text{2}\text{equiv}\right)$ leads to the formation of an alkyl lithium. When alkyl lithium is further treated with $\text{CuI}$$\left(\text{0}\text{.5}\text{equiv}\right)$, it leads to the formation of organocuprate reagent. The formed organocuprate reagent reacts with another organic halide to form the coupling product (new $\text{C}-\text{C}$ bond).

The corresponding reaction is shown below.

Figure 17

Thus, the product of the given reaction is,

Figure 18

Conclusion

The product of the given reaction is drawn in Figure 18.

Interpretation Introduction

(j)

Interpretation: The product formed in the given reaction is to be drawn.

Concept introduction: The treatment of an organic halide $\left({\text{R}}^{\text{'}}\text{X}\right)$ with an organoborane reagent $\left({\text{RBY}}_{\text{2}}\right)$ in the presence of $\text{Pd}$ catalyst to afford the $\text{C}-\text{C}$ coupling is known as Suzuki reaction. During reaction, the metal catalyst is coordinated with some ligands, like ${\text{PPh}}_{\text{3}}$. The reaction is facilitated in the presence of strong inorganic base like ${\text{NaOCH}}_{\text{2}}{\text{CH}}_{\text{3}}$ or $\text{NaOH}$.

Answer to Problem 26.32P

The product of the given reaction is,

Explanation of Solution

The given reaction involves treatment of an alkyne with an vinylborane, followed by treatment with organic halide in the presence of $\text{Pd}{\left({\text{PPh}}_{\text{3}}\right)}_{\text{4}}$ and $\text{NaOH}$.

The treatment of given alkyne with catecholborane leads to the formation of corresponding vinylborane in first step. This vinylborane (an organoborane) is formed by hydroboration which adds $\text{H}$ and $\text{B}$ elements in syn fashion. The further reaction is Suzuki, which involves treatment with organic halide in the presence of $\text{Pd}{\left({\text{PPh}}_{\text{3}}\right)}_{\text{4}}$ and $\text{NaOH}$.

The treatment of an organic halide $\left({\text{R}}^{\text{'}}\text{X}\right)$ with an organoborane reagent $\left({\text{RBY}}_{\text{2}}\right)$ in the presence of $\text{Pd}$ catalyst to afford the $\text{C}-\text{C}$ coupling is known as Suzuki reaction. During reaction, the metal catalyst is coordinated with some ligands, like ${\text{PPh}}_{\text{3}}$. The reaction is facilitated in the presence of strong inorganic base like ${\text{NaOCH}}_{\text{2}}{\text{CH}}_{\text{3}}$ or $\text{NaOH}$.

The corresponding reaction is shown below.

Figure 19

Thus, the product of the given reaction is,

Figure 20

Conclusion

The product of the given reaction is drawn in Figure 20.