699005-11-3

Upstream product

• 22979-35-7 Methyl phenyldiazoacetate 
• 1066-54-2 trimethylsilylacetylene 
• 101-41-7 benzeneacetic acid methyl ester 

Downstream Products

• 57200-23-4 3-phenyl-2(5H)-furanone 
• 39891-79-7 methyl 1H-indene-3-carboxylate 

Relevant academic research and scientific papers

Synthesis of Quinolines via the Metal-free Visible-Light-Mediated Radical Azidation of Cyclopropenes

We report the synthesis of quinolines using cyclopropenes and an azidobenziodazolone (ABZ) hypervalent iodine reagent as an azide radical source under visible-light irradiation. Multisubstituted quinoline products were obtained in 34-81% yield. The reaction was most efficient for 3-trifluoromethylcyclopropenes, affording valuable 4-trifluoromethylquinolines. The transformation probably proceeds through the cyclization of an iminyl radical formed by the addition of the azide radical on the cyclopropene double bond, followed by ring-opening and fragmentation.

CoIII-Catalyzed C-H Alkenylation and Allylation with Cyclopropenes via Sequential C-H/C-C Bond Activation

An atom-economical strategy for the C-H alkenylation and C-H allylation of arenes by employing cyclopropenes as versatile alkenylating and allylating reagents is reported, catalyzed by cobalt. The Co-catalyzed C-H alkenylation process involves sequential

Diastereoselective Trapping of Transient Carboxylic Oxonium Ylides with α,β-Unsaturated 2-Acyl Imidazoles

By developing a diastereoselective reaction of cyclopropene carboxylic acids with α,β-unsaturated 2-acyl imidazoles, we reported here a Michael-type trapping of transient carboxylic oxonium ylides. This transformation provides a direct approach for the construction of valuable γ-butenolide derivatives in good yields (60–99%) with high diastereoselectivities (up to >95:5 dr) under mild reaction conditions. (Figure presented.).

Blue-Light-Induced Carbene-Transfer Reactions of Diazoalkanes

Carbenes are very important reactive intermediates to access a variety of complex molecules and are applied widely in organic synthesis and drug discovery. Typically, their chemistry is accessed by the use of transition metal catalysts. Herein, we describe the application of low-energy blue light for the photochemical generation of carbenes from donor–acceptor diazoalkanes. This catalyst-free and operationally simple approach enables highly efficient cyclopropenation reactions with alkynes and the rearrangement of sulfides under mild reaction conditions, which can be utilized for both batch and continuous-flow processes.

Enantioselective, facially selective carbomagnesation of cyclopropenes

Described is the facially selective and enantioselective addition of carbon nucleophiles to prochiral 3-hydroxymethylcyclopropenes. The process creates up to four stereocenters in a tandem addition/capture sequence that combines three simple materials to give complex and diverse products. The asymmetry is induced by the inexpensive and recoverable ligand (S)-N-methylprolinol. The enantioselectivity (90-98% ee with MeMgCl) is high for a range of cyclopropenes and electrophiles. Importantly, the diastereoselectivity is complementary to that obtained by enantioselective cyclopropanation with aryldiazoacetates. High enantioselectivities are obtained only when methoxide is included in the reaction. Evidence is provided that at least two chiral ligands are involved in the enantioselectivity-determining step. Copyright

Simple large-scale preparation of 3,3-disubstituted cyclopropenes: Easy access to stereodefined cyclopropylmetals via transition metal-catalyzed hydrometalation

3,3-Disubstituted cyclopropenes have been readily prepared in a multigram scale via two different methods: (1) dehydrohalogenation of bromocyclopropanes, and (2) Rh-catalyzed addition of carbenoids to trimethylsilylacetylene followed by desilylation. Highly diastereoselective Pd-catalyzed hydrostannation and highly enantioselective Rh-catalyzed hydroboration of 3,3-disubstituted cyclopropenes afforded useful cyclopropylmetal building blocks in high yields.

Catalytic enantioselective hydroboration of cyclopropenes

2,2-Disubstituted cyclopropyl boronates have been synthesized with high degrees of diastereo- and enantioselectivity via the rhodium-catalyzed asymmetric hydroboration of 3,3-disubstituted cyclopropenes. A strong directing effect of ester and alkoxymethyl substituents has been demonstrated. The directing effect was found to be necessary in achieving high degrees of enantiomeric induction. Selected cyclopropylboronic derivatives were successfully employed in the Suzuki cross-coupling reaction to produce the corresponding optically active aryl- and vinylcyclopropanes in good yields. Copyright