Prilezhaev Reaction

Schematic representation of the Prilezhaev Reaction.

Mechanism of the Prilezhaev Reaction

Mechanism of the Prilezhaev Reaction

Original publication	Ber. Dtsch. Chem. Ges.. 1909, 42, 4811. Org. Lett.. 2003, 5, 4665.
Reviews	Acc. Chem. Res.. 1999, 32, 703. Org. React.. 1953, 7, 378.

Sample reactions

intermediate structure

AcOOH, NaOAc

AcOH, H2O

RT to 80 °C, 16 h, 85% (2 steps)

intermediate structure

intermediate structure

AcOOH, Na2HPO4

DCE

4 °C, 15 h

intermediate structure

intermediate structure

intermediate structure

AcOOH, Na2HPO4

DCE

RT

intermediate structure

intermediate structure

intermediate structure

mCPBA

CH2Cl2

RT, 2 h

intermediate structure

intermediate structure

mCPBA

CH2Cl2

RT, 2 h

intermediate structure

intermediate structure

mCPBA

CHCl3

80% (2 steps)

intermediate structure

intermediate structure

mCPBA, NaHCO3

CH2Cl2

RT, 11 h, 80%

intermediate structure

intermediate structure

mCPBA, NaHCO3

CH2Cl2

RT, 10.5 h, 45%

intermediate structure

intermediate structure

mCPBA, Na2CO3

CH2Cl2

-78 to -15 °C, 14 h

intermediate structure

intermediate structure

mCPBA

CH2Cl2

10 °C to RT, , 89%

"Mixture of isomers."

intermediate structure

intermediate structure

mCPBA

CH2Cl2

74%

intermediate structure

intermediate structure

mCPBA, NaHCO3

CH2Cl2

RT, 15 h, 81%

intermediate structure

intermediate structure

Camphorsulfonic acid

CH2Cl2

0 °C, , 60%

intermediate structure

intermediate structure

mCPBA

CH2Cl2

0 °C, 2 h, 92%

intermediate structure

intermediate structure

mCPBA, NaHCO3

CH2Cl2

-20 °C, 30 min

intermediate structure

intermediate structure

mCPBA

CHCl3

0 °C to RT, ON, 100%

intermediate structure

intermediate structure

AcOOH, NaOAc

AcOH, CH2Cl2

92%

intermediate structure

intermediate structure

mCPBA, NaOAc

CH2Cl2

RT, 24 h

intermediate structure

intermediate structure

mCPBA, NaHCO3

CH2Cl2

80%

intermediate structure

intermediate structure

mCPBA

DCE

40 °C, 24 h, 84%

intermediate structure

intermediate structure

mCPBA

CH2Cl2

RT, 30 min, 98%

intermediate structure

intermediate structure

NaHCO3, MMPP

Sealed tube

MeOH

110 °C, 7 d, 22% (α), 65 % (β)

"The yield were 67% (α) and 93 % (β) brsm."

intermediate structure

intermediate structure

mCPBA

CH2Cl2

0 °C to RT, 16 h, 85%

intermediate structure

intermediate structure

intermediate structure

mCPBA

CH2Cl2, Buffer (pH = 6.5)

RT, 2 h

intermediate structure

intermediate structure

AcOOH, Na2CO3

CH2Cl2

RT, 24 h, 68%

intermediate structure

intermediate structure

mCPBA, Na3PO4

CH2Cl2, H2O

RT, 24 h, 73%

intermediate structure

intermediate structure

mCPBA, NaHCO3

CH2Cl2

RT, 72 h, 86%

intermediate structure

intermediate structure

mCPBA, NaOAc

CH2Cl2

-20 to 0 °C, 90 min

intermediate structure