1352653-03-2

Upstream product

• 3485-84-5 N-vinylphthalimide 
• 6773-29-1 dimethyl diazomalonate 

Downstream Products

• 1356460-11-1 dimethyl 2-(2-(1,3-dioxoisoindolin-2-yl)-4-oxo-4-phenylbutyl)malonate 

Relevant academic research and scientific papers

An Expeditious Route to trans-Configured Tetrahydrothiophenes Enabled by Fe(OTf)3-Catalyzed [3+2] Cycloaddition of Donor–Acceptor Cyclopropanes with Thionoesters

A synthetic route to trans-configured tetrahydrothiophenes (THTs) through Fe(OTf)3-promoted [3+2] cycloaddition of donor–acceptor cyclopropanes with thionoesters was developed. The cycloaddition proceeded in high yield with high diastereoselectivity, affording transient α-alkoxy THTs. Not only aromatic and aliphatic thionoesters, but also thionolactone were applicable to the present iron catalysis. Further transformation of the S,O-ketal functionality of the product was achieved in a highly trans diastereoselective manner. Moreover, the utility of our methodology was clearly demonstrated by the synthesis of enantioenriched trans-configured THTs.

Catalytic enantiospecific [3+2] annulation of aminocyclopropanes with ketones

An almost familiar ring: The first enantiospecific [3+2] annulation of donor-acceptor aminocyclopropanes with ketones is reported (see scheme; Phth=phthaloyl). The reaction is catalysed by tin(IV) chloride (5 mol%) at -78°C and gives aminotetrahydrofurans bearing a quaternary C5 atom in high yield, diastereoselectivity and enantiospecificity (see scheme). Copyright

(3+2)-Cycloaddition of Donor-Acceptor Cyclopropanes with Thiocyanate: A Facile and Efficient Synthesis of 2-Amino-4,5-dihydrothiophenes

An easy and efficient route to obtain 2-amino-4,5-dihydrothiophenes is presented. A formal (3+2)-cycloaddition of donor-acceptor cyclopropanes and ammonium thiocyanate catalyzed by Yb(OTf) 3delivers the desired products in good to excellent yields. A broad range of functional groups is tolerated during this process.

Divergent Reactivity of Thioalkynes in Lewis Acid Catalyzed Annulations with Donor–Acceptor Cyclopropanes

Efficient methods for the convergent synthesis of (poly)cyclic scaffolds are urgently needed in synthetic and medicinal chemistry. Herein, we describe new annulation reactions of thioalkynes with phthalimide-substituted donor–acceptor cyclopropanes, which gave access to highly substituted cyclopentenes and polycyclic ring systems. With silyl-thioalkynes, the Lewis acid catalyzed [3+2] annulation reaction with donor–acceptor cyclopropanes took place to afford 1-thio-cyclopenten-3-amines. On the other hand, an unprecedented polycyclic compound was formed with alkyl-thioalkynes through a reaction pathway directly involving the phthalimide group. The two transformations proceeded in good yields and tolerated a large variety of functional groups.

Dynamic kinetic asymmetric [3 + 2] annulation reactions of aminocyclopropanes

We report the first example of a dynamic kinetic asymmetric [3 + 2] annulation reaction of aminocyclopropanes with both enol ethers and aldehydes. Using a Cu catalyst and a commercially available bisoxazoline ligand, cyclopentyl- and tetrahydrofurylamines were obtained in 69-99% yield and up to a 98:2 enantiomeric ratio using the same reaction conditions. The method gives access to important enantio-enriched nitrogen building blocks for the synthesis of bioactive compounds.

Ring-opening 1,3-dichlorination of donor-acceptor cyclopropanes by iodobenzene dichloride

Donor-acceptor cyclopropanes are reacted with iodobenzene dichloride to afford ring-opened products bearing chlorine atoms in the 1- and 3-positions, adjacent to the donor and acceptor groups. A variety of different donors (e.g., alkyl, aryl, N, and O) and acceptor moieties (e.g., ketones, diesters, and dinitriles) are used.

Catalytic Friedel-Crafts reaction of aminocyclopropanes

A Lewis acid catalyzed Friedel-Crafts reaction between donor-acceptor aminocyclopropanes and indoles and other electron-rich aromatic compounds is reported. Indole alkylation at the C3 position was generally obtained for a broad range of functional groups and substitution patterns. In the case of C3-substituted indoles, C2 alkylation was observed. The reaction gives a rapid access to gamma amino acid derivatives present in numerous bioactive molecules.

Iron-catalyzed [3 + 2] annulation of aminocyclopropanes with aldehydes: Stereoselective synthesis of aminotetrahydrofurans

The first method for the [3 + 2] annulation of donor-acceptor aminocyclopropanes with aldehydes is reported. The reaction is catalyzed by iron trichloride on alumina in yields up to 99% and with excellent cis selectivities (up to >20:1) and represents a stereoselective and atom economic access to valuable 2-aminotetrahydrofurans, which constitute the core of DNA and RNA.

Catalytic [3+2] annulation of aminocyclopropanes for the enantiospecific synthesis of cyclopentylamines

With nitrogen too: The first catalytic [3+2] annulation of aminocyclopropanes with enol ethers is reported (see scheme; Phth=phthaloyl). The reaction worked with easily accessible phthalimidocyclopropanes using 5 mol % of SnCl4 in nearly quantitative yields. Polysubstituted cyclopentylamines, which are often present in bioactive compounds, were obtained with high diastereoselectivity and enantiospecificity. Copyright