4.2.8. Reductive Coupling 3109 5. Reaction of Aromatic Compounds 3110 5.1. Electrophilic Substitutions 3110 5.2. Radical Substitution 3111 5.3. Oxidative Coupling 3111 5.4. Photochemical Reactions 3111 6. Reaction of Carbonyl Compounds 3111 6.1. Nucleophilic Additions 3111 6.1.1. Allylation 3111 6.1.2. Propargylation 3120 6.1.3. Benzylation 3121 6.1.4. Arylation/Vinylation 3121 6.1.5. Alkynylation 3121 6.1.6. Alkylation 3121 6.1.7. Reformatsky-Type Reaction 3122 6.1.8. Direct Aldol Reaction 3122 6.1.9. Mukaiyama Aldol Reaction 3124 6.1.10. Hydrogen Cyanide Addition 3125 6.2. Pinacol Coupling 3126 6.3. Wittig Reactions 3126 7. Reaction of R,â-Unsaturated Carbonyl Compounds 3127

Organic Reactions in Aqueous Media with a Focus on Carbon−Carbon Bond Formations: A Decade Update

Methodology for the construction of quaternary carbon centers

An asymmetric synthesis of the fugu fish poison, (−)-tetrodotoxin, is described. The route to this extraordinary target employs a number of unique transformations, foremost of which are two stereospecific C−H bond functionalization reactions. Accordingly, Rh-catalyzed carbene and nitrene C−H insertions facilitate rapid entry to the cyclohexane core of the natural product and make possible the late-stage installation of the tetrasubstituted carbinolamine center.

A stereoselective synthesis of (-)-tetrodotoxin.

b. Ring Closures of the Two-Carbon Bridge 42 c. Ring Closures of the One-Carbon Bridge 44 9. Free Radical-based Methods 44 a. Reductive Methods 44 b. Oxidative Methods 47 10. Organometallic-Based Methods 48 a. Iron Carbonyl Chemistry 48 b. Palladium Chemistry 49 11. Miscellaneous Methods 50 a. Wittig Olefination 50 b. Photochemical Rearrangements 51 c. Prins Reaction 51 IV. Cycloadditions and Other Electrocyclizations 51 1. [4+2] Cycloadditions 51 2. [5+2] Cycloadditions 52 3. [4+3] Cycloadditions 53 4. [3+2] Cycloadditions 54 5. [2+2+2] Cycloadditions 54 6. Ene-Type Cyclizations 54 7. Sigmatropic Rearrangements 55 V. Ring Expansion of Bicyclo[2.2.1]heptanes 55 VI. Rearrangement of Polycyclic Intermediates 58 1. Isomerization of Bicyclo[2.2.2]octanes 58 2. From Cyclopropane-Containing Intermediates 60 3. From Cyclobutane-Containing Intermediates 61 4. From Bridged Bicyclononane Precursors 62 VII. Reactivity 63 1. Fragmentations Leading to Nonbridged Carbocycles 63

Synthesis of Functionalized Bicyclo[3.2.1]octanes and Their Multiple Uses in Organic Chemistry.

Ein neues Jahrtausend hat begonnen – Grund genug, sich die Frage zu stellen, welchen Stand die Totalsynthese von Naturstoffen erreicht hat. Dieser Aufsatz mochte eine Antwort geben, indem er die Entwicklung dieser chemischen Disziplin, die Aspekte von exakter Wissenschaft und schoner Kunst in sich vereint, von Anbeginn bis in die heutige Zeit beschreibt; es wird geschildert, wie viel wir in der Wissenschaft der Totalsynthese schon erreicht haben, aber auch, dass dieses Forschungsgebiet den Kinderschuhen gerade erst entschlupft.

Alex Andrus

Papers

Stereospecific total synthesis of aphidicolin

Total synthesis of aphidicolin

Cyclocarbonylation of unsaturated tosylates as a method of cyclanone synthesis

Stereospecific total synthesis of aphidicolin

Synthesis of 3-methylphosphonylthienamycin and related 3-phosphonylcarbapenems