p. 566

O

CHH

Formaldehyde

O

CCH3H

Acetaldehyde

CH

O

Benzaldehyde

Common Names of Simple Aldehydes and Ketones

p. 566

Common Names of Carbonyl substituents

p. 567

Preparation of Aldehydes and Ketones : Review

1. Oxidation of 1 alcohols to aldehydes:a. PCCb. Dess-Martin Periodinane

p. 567

Preparation of Aldehydes and Ketones : Review

1. Oxidation of 1 alcohols to aldehydes:a. PCCb. Dess-Martin Periodinane

p. 567

Preparation of Aldehydes and Ketones : Review

2. Oxidation of 2 alcohols to ketones:a. CrO3 , H2SO4 b. K2Cr2O7, H2SO4 c. PCCd. Dess - Martin

p. 567

Preparation of Aldehydes and Ketones : Review

2. Oxidation of 2 alcohols to ketones:a. CrO3 , H2SO4 b. K2Cr2O7, H2SO4 c. PCCd. Dess - Martin

p. 568

Preparation of Aldehydes and Ketones : Review

3. Aryl aldehydes and ketones:Friedel – Crafts Acylation

p. 568

Preparation of Aldehydes and Ketones : Review

3. Aryl aldehydes and ketones:Friedel – Crafts Acylation

p. 568

Preparation of Aldehydes and Ketones: New

1. From Acid Chlorides via Acyl TransferUsing R2CuLi (Section 16.4)

p. 568

Preparation of Aldehydes and Ketones: New

1. From Acid Chlorides via Acyl TransferUsing R2CuLi (Section 16.4)

2. From EstersReduction with DIBAH (Section 16.6)

p. 568

Oxidation of Aldehydes : Review

a. CrO3, H2SO4

b. K2Cr2O7, H2SO4

p. 568

Oxidation of Aldehydes : Review

a. CrO3, H2SO4

b. K2Cr2O7, H2SO4

Fig. 14-3, p. 571

Nucleophilic Additions to Aldehydes and Ketones

I. Reactivity

1. Aldehydes vs. ketones

2. Aromatic vs. aliphatic

p. 571

Fig. 14-3, p. 571

Nucleophilic Additions to Aldehydes and Ketones

I. Reactivity

1. Aldehydes vs. ketones

2. Aromatic vs. aliphatic

3. The Burgi – Dunitz angle

Fig. 14-3, p. 571

Nucleophilic Additions to Aldehydes and Ketones

The Burgi-Dunitz(-Lehn-Wipff) Angle:Molecular orbital representaiton

Tetrahedron 1974 30 (12): 1563–1572.

Fig. 14-3, p. 571

Nucleophilic Additions to Aldehydes and Ketones

II. Types of Nucleophiles

1. Anionic

2. Neutral

Fig. 14-3, p. 571

Nucleophilic Additions to Aldehydes and Ketones

II. Types of Nucleophiles

1. Anionic

2. Neutral

i. Water

ii. Alcohols

iii. 1 amines

iv. 2 amines

Professor Gilbert Stork

Stork was born in Brussels, Belgium, and received his secondary education in France. The B.S. (1942) and Ph.D. (1945) were obtained at the Universities of Florida and Wisconsin respectively. He was on the Harvard faculty (1946-53), then joined the Columbia faculty where he was instrumental in building its strong organic group and is currently Eugene Higgins Professor Emeritus. Stork's many awards include the ACS Award in Pure Chemistry (1957), the ACS Award for Creative Work in Synthetic Organic Chemistry (1967), the Arthur C. Cope Award (1980), the Willard Gibbs Medal (1982), the National Medal of Science (1982), the Tetrahedron Prize (1985), the Roger Adams Award (1991) and the Wolf Prize (1996). In 2001 he published the first completely stereoselective total synthesis of quinine.

http://chem.tufts.edu/AMichael-Bio.html

Fig. 14-3, p. 571

Reactions of Ylides with Aldehydes

I. The Wittig Reaction

1. Generation and nature of ylides

2. The Metathesis reaction

a. Stereochemistry

The Truth about the Wittig reaction

J. Am. Chem. Soc. 1973, 95, 5778.

PhPh Ph

H CH3

R

HPhPh Ph

H CH3

H

RPhPh Ph

H3C H

H

R

steric interaction betweenH and CH3

steric interaction betweenR and CH3

Alternative 2 + 2 transition states

• may lead to trans prod

steric interaction betweenR and Ph

PhPh Ph

H3C H

R

H

HH

H3C R

OP

Ph Ph

Phfast

H3C R0 °C toroom temp.

-78 °Cirreversible

slow

Fig. 14-3, p. 571

Reactivity of -unsaturated carbonly compounds

1. Electrophilic sites

2. Hard-soft acid-base theory

3. Examples

p. 589

Professor Author Michael

Born in Buffalo NY in 1855, he studied chemistry at Heidelberg under Robert Bunsen (1811-1899) and at Berlin under August Wilhelm Hofmann (1818-1892). He then studied under Adolphe Wurtz (1817-1884) in Paris and Dimitri Ivanoviè Mendeleev (1834-1907) in St Petersburg, but never bothered to take a degree. He was made Professor of Chemistry at Tufts College near Boston. In 1889, he married one of his most brilliant students, (1857-1904), one of the few women organic chemists Helen Cecilia DeSilver Abbott in this period. After a failed attempt to run the chemistry department at Clark University in Worcester, Massachusetts, in 1891, he spent three years working with his wife in his private laboratory on the Isle of Wight before returning to Tufts. After he retired from Tufts in 1907, Michael set up another private laboratory at Newton Center near Boston. In 1912 he was appointed a Professor of Chemistry, without lecturing duties, at Harvard University. Arthur Michael died in 1942.

http://chem.tufts.edu/AMichael-Bio.html

Professor Henry Gilman

(May 9, 1893 – Nov 7, 1986). Born in Boston, Massachusetts, he received  his B. S. (1915), an M. S.  (1916), and a Ph.D. (1918) in Chemistry from Harvard University. For his pre-doctoral work he studied in Europe at Zurich Polytechnikum, the Sorbonne in Paris, and at Oxford in London. Dr. Gilman began his career at the University of Illinois as an Instructor of Chemistry in 1919. Later that year, he accepted the position of Assistant Professor (1919 - 1920) at Iowa State College (University). By 1923 Dr. Gilman had been promoted to full Professor teaching all the Organic Chemistry courses at Iowa State College.

His main area of research was in the Organometallic Chemistry area of Grignard reagents where he developed numerous Organometallic reagents, including the dialkyllithium reagent which bears his name.

http://www.lib.iastate.edu/spcl/exhibits/150/template/gilman.html

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