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Great and complete organic chemistry lecture notes
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Chemistry 432 – Lecture Notes Updated: Spring 2016
Course Organization: Things You Need to Know
Nucleophiles and Electrophiles: The Basis of Organic Chemistry
Synthesis 1: Strychnine
Woodward, 1954
Reactions: · Fischer indole synthesis · Indole addition · Dieckmann condensation · Allylic rearrangement
Concepts: · Retrosynthesis · Substructure Recognition notes_
Properties: · A poison from Southeast Asian rainforests · Known in Europe from the 16th^ century · Isolation in 1818 (Pelletier and Caventou) · Structure determined in 1946; X-ray in 1956 · 6 contiguous stereocentres!
Definition:
Retrosynthesis - A technique for transforming the structure of a synthetic target into a sequence of simpler structures, along a pathway which ultimately leads to known or commercially available starting materials.
notes_
Continuing Steps:
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Other Syntheses of Strychnine:
Magnus, 1992 – J.Am.Chem.Soc. 1992 , 4403. - 38 years from 1st^ to 2nd^ synthesis! Stork, 1992 – lecture (Iscia Porto, Italy). Kuehne, 1993 – J.Org.Chem. 1993 , 7490. Overman, 1993 – J.Am.Chem.Soc. 1993 , 9293. - 1st enantioselective synthesis Rawal, 1994 – J.Org.Chem. 1994 , 2685. Martin, 1996 – J.Am.Chem.Soc. 1996 , 9804. Bonjoch, 1999 – Angew.Chem.Int.Ed. 1999 , 395. Vollhardt, 2000 – Org.Lett. 2000 , 2479. Shibasaki, 2002 – J.Am.Chem.Soc. 2002 , 14546. Mori, 2002 – Angew.Chem.Int.Ed. 2002 , 1934. Bodwell, 2002 – Angew.Chem.Int.Ed. 2002 , 3261. Fukuyama, 2004 – J.Am.Chem.Soc. 2004 , 10246. Padwa, 2007 – Org.Lett. 2007 , 279. Andrade, 2010 – J.Org.Chem. 2010 , 3529. Vanderwal, 2010 – ACS abstratcts MacMillan, 2010 – ACS abstracts Reissig, 2010 – Angew. Chem. Int. Ed. 2010 , 8021. … and many others since! …
Synthesis 2: Progesterone
Marker, 1943
Reactions: · Oxidative degradations · General metal oxide degradations · Lemieux-Von Rudloff oxidation · Ozonolysis · Jones oxidation
Concepts: · Semisynthesis notes_
Properties: · Steroid hormone involved in menstruation · Orally available analogues administered along with estrogen as the birth-control pill.
The problem of access to progesterone for medical studies was solved by Marker’s isolation of diosgenin in large quantities from a Mexican yam.
Synthesis:
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Synthesis 3: Prostaglandin E 2
Corey, 1969 and onward
Reactions: · General discussion of olefin-forming reactions: · Wittig reaction · Horner-Wadsworth Emmons reaction · Still-Gennari olefination · Julia olefination · Corey-Winter olefination · Peterson olefination · Barton-Kellog extrusion reaction · Asymmetric Diels-Alder reaction · Baeyer-Villiger oxidation · CBS reduction · Iodolactonization
Properties: · The prostaglandins are a large family of lipophilic C-20 hormones. · Isolated in the 1930’s, structures in 1960’s. · Originate from action of COX1 and COX2 on arachidonic acid. (aspirin targets both enzymes, vioxx selectively targets COX2) · Various prostaglandins may control: cell growth hormone regulation inflammation sensitivity to pain constriction / dilation of muscle cells · PGE 2 and PGF 2 are used to induce childbirth or abortion
Synthetic Strategies:
notes_ Retrosynthesis:
notes_
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Synthesis 4: Periplanone B
Still, 1979 (largely credited with the invention of flash chromatography)
Classics, I, 211
Reactions: · Anionic oxy-Cope · Rubottom oxidation · Selective epoxidations
Concepts: notes_ · Use of medium- or large-ring conformation to control stereochemistry
Retrosynthesis:
notes_
Methodology:
4.1 Cope-type reactions:
Methodology 5.1. The Stille, Suzuki & Negishi reactions - Related Mechanisms
notes_
Methodology 5.2. The Heck reaction:
