Organometallics

Question 1

Cuprate w/ alpha-beta unsaturated ketone

Answer 1

Addition to beta carbon

Question 2

Simmons-Smith (reagent prep)

Answer 2

CH2I2 + Zn-Cu, Et2O → ICH2ZnI

Question 3

Grignards (prep)

Answer 3

R-X + Mg, THF

Question 4

Cuprates (prep)

Answer 4

R-Li, CuX (0.5 eq), THF

Question 5

Negishi (reagent prep)

Answer 5

ZnCl2 + R-Li → RZnCl

Question 6

Stille: Mechanism Steps

Answer 6

Oxidative addition, transmetallation, reductive elimination

Question 7

Stille (rxn)

Answer 7

R’-X + Bu3SnR + Pd(PPh3)4 → R’-R + Pd(Ph3)4

Question 8

Negishi: Mechanism Steps

Answer 8

Oxidative addition, transmetallation, reductive elimination

Question 9

Suzuki: Mechanism Steps

Answer 9

Oxidative addition, ligand displacement, transmetallation, reductive elimination

Question 10

Stille (reagent prep)

Answer 10

RMgX + Bu3SnCl → BuSn3R (+ MgX)

Question 11

Organolithium (prep)

Answer 11

R-X + 2 Li, THF

Question 12

Cuprate w/ acid halide

Answer 12

Ketone

Question 13

Heck: Mechanism Steps

Answer 13

Oxidative addition, syn-addition, C-C bond rotation, syn-elimination, reductive elimination

Question 14

Alkene Metathesis

Answer 14

Two alkenes swap sides w/ Grubbs or Schrock cat.

Question 15

Suzuki (rxn)

Answer 15

R’-X + RBY2 + NaOEt + Pd(PPh3)4 → R’-X + Pd(PPh3)4

Question 16

Cory-Posner / Whitesides-House

Answer 16

R2CuLi + R’-X, THF → R-R’

Question 17

Simmons-Smith (rxn)

Answer 17

ICH2ZnI + alkene → cyclopropane

Question 18

Dichlorocarbene (rxn)

Answer 18

:CCl2 + alkene → cyclopropane w/ Cl2 on the added carbon

Question 19

Dichlorocarbene (prep)

Answer 19

CHCl3 + KOt-Bu → :CCl2

Question 20

Negishi (rxn)

Answer 20

R’-X + R-ZnX + Pd(PPh3)4 → R’-R + Pd(PPh3)4

Question 21

Heck

Answer 21

R-X + alkene w/ vinyl proton + NaOAc + Pd(PPh3)4 → R-alkene (replace H) + Pd(PPh3)4