Highly Cited Contributions FromEJ Corey

John HayesGroup Meeting Special Topic

8/26/15

Biography

• Born July 12, 1928• Undergrad: MIT• Ph.D.: MIT, John C. Sheehan• 1956: University of Illinois,

Urbana-Champaign• 1959: Harvard University• Awards• Notable Students

Scope of Accomplishments

• 1105 publications in 2014 (+ 7 not updated)– Ejcorey.org

• 17 Unique Methods Between 1950 and 2003– Including: Corey-Chaykovsky, PCC Oxidation

• >260 Total Syntheses• At least 5 books with numerous forewords authored

Corey-Bakshi-Shibata (CBS) Reagent

Corey, E.J., JACS, 1987, 109, 5551.

TBS Protecting Group

• Orthogonal to -OBn, O-trichloroethyl, and tetrahydropyran (THP)

• More stable silyl ether than TMS and dimethylisopropylsilyl ether

• First time used imidazole and DMF

Corey, E.J., JACS, 1972, 94, 6190.

Corey-Chaykovsky Reaction

• First use in ring expansions and homologations

• Dimethyloxosulfonium vs. Dimethylsulfonium

Corey, E.J., JACS, 1965, 87, 1353.

Enantioselective Phase Transfer Catalysis

Corey, E.J., JACS, 1997, 119, 12414.

Corey-Fuchs Reaction

• Conversion of aldehydes to terminal alkynes

• 1st Step: Wittig with CBr4

• 2nd Step: Deprotonation and Lithium-Halogen Exchange

Corey, E.J., Tet. Lett., 1972, 13, 3769.

PCC Oxidation

Corey, E.J., Tet. Lett., 1975, 31, 2647.

Enantioselective Synthesis of α-Amino Nitriles

Corey, E.J., Org. Lett., 1999, 1, 157.

Catalyst for Enantioselective Diels-Alder

• Catalyst produced in 3 steps from (S)-(+)-Phenylglycinol

• Diels-Alder experiments performed using Fe(III) halides with 4 and cyclopentadiene

Corey, E.J., JACS, 1991, 113, 729.

Enantioselective Synthesis of Amino Acids byChiral Phase Transfer Catalyst

Corey, E.J., Tet. Lett., 1998, 39, 5347.

PDC Oxidation

OH

OH O

O

OH O

86%

97%

92%

Corey, E.J., Tet. Lett., 1979, 5, 399.

Face-Selective Nitroaldol

Corey, E.J., ACIE, 1999, 111, 2057.

Enantioselective Total Synthesis of Ecteinascidin 743

Corey, E.J., JACS,1996, 118, 9202.

CuCl Accelerated Stille Couplings

Corey, E.J., JACS, 1999, 121, 7600.

Silylations with Trialkylsilyltriflates

• New method for producing TBSOTf and TIPSOTf

• Use of TBSOTf to silylate tertiary and unreactive secondary alcohols

• Use of TIPSOTf to trap enol ethers

• Improvement of silylation procedures for C18 HPLC columns

t-BuOH

2,6-lutidineTBSOTf OTBS

DCM90%

O Et3NTIPSOTf

Benzene>98%

OTIPS

OEt3N

TIPSOTf

Benzene

OTIPS

Corey, E.J., Tet. Lett., 1981, 82, 3455.

Oxidative Hydrolysis of Dithianes to Carbonyls

Corey, E.J., JOC, 1971, 36, 3553.

Acetoxylation and C-C Bond Formation at Unactivated Positions on α-Amino Acids

Corey, E.J., Org. Lett., 2006, 8, 3391.

Enantioselective Route to (S)-(-)-phenyloxirane

O

NH

CO2H aq. benzyl chloroformate

then MeOH, BF3·Et2O96%

NH

CO2Me 1. PhMgCl, THF, 52%

2. BH3, THFN

BH

O

PhPh

ClO

1. BH3, 1% catalyst, THF, 97%

2. aq. NaOH, 96%

Corey, E.J., JOC, 1988, 53, 2861.

Corey-Nicolaou Macrolactonization

OH

OH

O

n

N

S S N

PPh3

O

O

n

Corey, E.J., JACS, 1974, 96, 5614.

Enantioselective Diels-Alder and Aldol Reactions

Corey, E.J., JACS, 1989, 111, 5493.

Enantioselective Epoxidation of α,ß-Enones

Corey, E.J., Org. Lett., 1999, 1, 1287.

Super-Lewis Acidic Chiral Catalyst

Corey, E.J., JACS, 1996, 118, 5502.

Highly Cited Contributions FromEJ Corey

John HayesGroup Meeting Special Topic

8/26/15