Examination of nature's favorite molecules reveals a striking preference for making carbon-heteroatom bonds over carbon-carbon bonds-surely no surprise given that carbon dioxide is nature's starting material and that most reactions are performed in water. Nucleic acids, proteins, and polysaccharides are condensation polymers of small subunits stitched together by carbon-heteroatom bonds. Even the 35 or so building blocks from which these crucial molecules are made each contain, at most, six contiguous C-C bonds, except for the three aromatic amino acids. Taking our cue from nature's approach, we address here the development of a set of powerful, highly reliable, and selective reactions for the rapid synthesis of useful new compounds and combinatorial libraries through heteroatom links (C-X-C), an approach we call "click chemistry". Click chemistry is at once defined, enabled, and constrained by a handful of nearly perfect "spring-loaded" reactions. The stringent criteria for a process to earn click chemistry status are described along with examples of the molecular frameworks that are easily made using this spartan, but powerful, synthetic strategy.

https://www.onlinelibrary.wiley.com/doi/pdf/10.1002/1521-3773%2820010601%2940%3A11%3C2004%3A%3AAID-ANIE2004%3E3.0.CO%3B2-5

Click Chemistry: Diverse Chemical Function from a Few Good Reactions.

Betrachtet man die in der Natur am haufigsten vorkommenden Verbindungen, so fallt auf, dass die Bildung von Kohlenstoff-Heteroatom-Bindungen gegenuber der von Kohlenstoff-Kohlenstoff-Bindungen deutlich bevorzugt ist Da zum einen Kohlendioxid die Basisverbindung der Natur ist und andererseits das Medium naturlicher Reaktionen zumeist Wasser ist, uberrascht dies sicherlich nicht Nucleinsauren, Proteine und Polysaccharide sind polymere Kondensationsprodukte kleiner Untereinheiten, die durch Kohlenstoff-Heteroatom-Bindungen verknupft sind Sogar die etwa 35 Baueinheiten, aus denen diese essentiellen Verbindungen bestehen, enthalten nicht mehr als sechs aufeinander folgende C-C-Bindungen, sieht man einmal von den drei aromatischen Aminosauren ab Mit der Natur als Vorbild richteten wir unser Interesse auf die Entwicklung leistungsfahiger, gut funktionierender und selektiver Reaktionen fur die effiziente Synthese neuartiger nutzlicher Verbindungen sowie kombinatorischer Bibliotheken mittels Heteroatomverknupfungen (C-X-C) Diese Synthesestrategie nennen wir „Click-Chemie“ Click-Chemie ist durch eine Auswahl einiger weniger nahezu idealer Reaktionen charakterisiert, mit all ihren Grenzen und Moglichkeiten In diesem Beitrag werden zum einen die strengen Kriterien, die Reaktionen erfullen mussen, um die Bezeichnung „Click-Chemie“ zu verdienen, definiert, zum anderen werden Beispiele fur molekulare Strukturen gegeben, die mit dieser spartanischen, aber dennoch leistungsfahigen Synthesestrategie leicht hergestellt werden konnen

Click-Chemie: diverse chemische Funktionalität mit einer Handvoll guter Reaktionen

Claisen rearrangement over the past nine decades.

Recent developments in the stereoselective synthesis of α-aminoacids

(1990). The Shikimate Pathway — A Metabolic Tree with Many Branche. Critical Reviews in Biochemistry and Molecular Biology: Vol. 25, No. 5, pp. 307-384.

The shikimate pathway―a metabolic tree with many branches

Transformation of D-erythrose to some pseudoaldopentofuranoses. Syntheses of (1S,2R,3S,4S)-, (1R,2R,3S,4S)-, and (1R,2S,3S,4S)-2,3,4-trihydroxy-1-(hydroxymethyl)cyclopentanes and (1R,2S,3R,4R)-2,3-dihydroxy-4-(hydroxymethyl)-1-cyclopentanamine

Chemical modification of β-glucocerebrosidase inhibitor N-octyl-β-valienamine: synthesis and biological evaluation of N-alkanoyl and N-alkyl derivatives

Enantiospecific total synthesis of (+)-altholactone [(+)-goniothalenol] (1), a novel tetrahydrofuropyran-5-one possessing significant cytotoxicity against several tumor cell lines, has been achieved by using L-arabinose as the redundant starting material The pivotal tetrahydrofuran formation was realized by treatment of the diastereomeric mixture of (2S,3R)-4,5-epoxy-5-phenyl-1,2,3-pentanetriol 1,3-benzylidene acetals 8 and 8′ with silica gel Simultaneous stereochemical inversion at C-4 and C-5 of the major cyclization product, O,O′-benzylidene derivative of (2S,3R,4S,5S)-2-(hydroxymethyl)-5-phenyltetrahydrofuran-3,4-diol (11), to the 2S,3R,4R,5R diastereomer 10 was achieved by hydroboration of (2S,3S)-3-hydroxy-2-(hydroxymethyl)-5-phenyl-2,3-dihydrofuran O,O′-benzylidene derivative (18) which derived from 11 Pfitzner-Moffatt oxidation of 10 followed by NaBH4 reduction gave the 2S,3R,4S,5R diastereomer 20 exclusively Displacement of the triflate group in (2S,3R,4S,5S)-2-(hydroxymethyl)-5-phenyl-4-[(tr

Total Syntheses of (+)-Altholactone [(+)-Goniothalenol] and Three Stereocongeners and Their Cytotoxicity against Several Tumor Cell Lines

Synthesis of beta-D-GlcpNAc-(1-->2)-5a-carba-alpha-D-Man p-(1-->6)-beta-D- Glcp-O(CH2)7CH3: a reactive acceptor analog for N-acetylglucosaminyltransferase-V.

muco-Inosamine-1, scyllo-inosamine, muco-inosadiamine-1,5 and myo-inosadiamine-1,2 have been synthesized from myo-inositol. Their structures have also been established by a study of the NMR spectra of their acetyl derivatives. When 1, 4, 5, 6-tetra-O-acetyl-3-O-mesyl-myo-inositol is treated with sodium azide in boiling aqueous 2-methoxyethanol, an azido derivative is obtained. The azido compound is hydrogenated in the presence of a catalyst and subsequently acetylated to give muco-inosamine-1. The stereochemical course of the reaction has been proposed to be an anchimeric reaction. When the analogous reaction is carried out with 2,3-di-O-mesyl-myo-inositol tetraacetate, myo-inosadiamine-1,2 or muco-inosadiamine-1,5 is obtained as the main product, depending on the solvent applied.

Seiichiro Ogawa

Papers

Transformation of D-erythrose to some pseudoaldopentofuranoses. Syntheses of (1S,2R,3S,4S)-, (1R,2R,3S,4S)-, and (1R,2S,3S,4S)-2,3,4-trihydroxy-1-(hydroxymethyl)cyclopentanes and (1R,2S,3R,4R)-2,3-dihydroxy-4-(hydroxymethyl)-1-cyclopentanamine

Chemical modification of β-glucocerebrosidase inhibitor N-octyl-β-valienamine: synthesis and biological evaluation of N-alkanoyl and N-alkyl derivatives

Total Syntheses of (+)-Altholactone [(+)-Goniothalenol] and Three Stereocongeners and Their Cytotoxicity against Several Tumor Cell Lines

Synthesis of beta-D-GlcpNAc-(1-->2)-5a-carba-alpha-D-Man p-(1-->6)-beta-D- Glcp-O(CH2)7CH3: a reactive acceptor analog for N-acetylglucosaminyltransferase-V.

Aminocyclitols. VIII. A Synthesis of Inosamines and Inosadiamines