87959-45-3

Upstream product

• 1195-32-0 1-methyl-4-isopropenylbenzene 
• 75-25-2 Bromoform 
• 122-00-9 para-methylacetophenone 

Downstream Products

• 1592-34-3 2,3-diethoxybutane 
• 59970-06-8 (Z)-1-(but-2-en-2-yl)-4-methylbenzene 
• 34815-65-1 (E)-1-(but-2-en-2-yl)-4-methylbenzene 
• 1064001-35-9 1-methyl-4-(1-methyl-2-cyclopropen-1-yl)benzene 

Relevant academic research and scientific papers

Enantioselective Hydrothiolation: Diverging Cyclopropenes through Ligand Control

In this article, we advance Rh-catalyzed hydrothiolation through the divergent reactivity of cyclopropenes. Cyclopropenes undergo hydrothiolation to provide cyclopropyl sulfides or allylic sulfides. The choice of bisphosphine ligand dictates whether the pathway involves ring-retention or ring-opening. Mechanistic studies reveal the origin for this switchable selectivity. Our results suggest the two pathways share a common cyclopropyl-Rh(III) intermediate. Electron-rich Josiphos ligands promote direct reductive elimination from this intermediate to afford cyclopropyl sulfides in high enantio- A nd diastereoselectivities. Alternatively, atropisomeric ligands (such as DTBM-BINAP) enable ring-opening from the cyclopropyl-Rh(III) intermediate to generate allylic sulfides with high enantio- A nd regiocontrol.

Stereoselective Synthesis of Vinylcyclopropa[ b]indolines via a Rh-Migration Strategy

A mild rhodium catalytic system has been developed to synthesize vinylcyclopropa[b]indolines through cyclopropanation of indoles with vinyl carbenoids generated from ring opening of cyclopropenes in situ. By employing a Rh-migration strategy, the products can be obtained with good to excellent E:Z ratios (≤99:1) and complete diastereoselectivity (≤99:1). This method is easy, has a low catalyst loading, and works for a broad range of functionalities.

A convenient access to allylic triflones with allenes and triflyl chloride in the presence of (EtO)2P(O)H

A simple method for the preparation of allylic triflones from allenes and triflyl chloride in the presence of (EtO)2P(O)H has been developed. The features of this reaction are catalyst-free and simple starting substrates. This method tolerates diverse functional groups and substituted allylic triflones are obtained in moderate to good yields.

Copper-Catalyzed Enantio- and Diastereoselective Addition of Silicon Nucleophiles to 3,3-Disubstituted Cyclopropenes

A highly stereocontrolled syn-addition of silicon nucleophiles across cyclopropenes with two different geminal substituents at C3 is reported. Diastereomeric ratios are excellent throughout (d.r.≥98:2) and enantiomeric excesses usually higher than 90 %, even reaching 99 %. This copper-catalyzed C?Si bond formation closes the gap of the direct synthesis of α-chiral cyclopropylsilanes.

Construction of All-Carbon Chiral Quaternary Centers through CuI-Catalyzed Enantioselective Reductive Hydroxymethylation of 1,1-Disubstituted Allenes with CO2

A catalytic enantioselective construction of all-carbon chiral quaternary centers through reductive hydroxymethylation of 1,1-disubstituted allenes with CO2 has been developed. In the presence of a copper/Mandyphos catalyst, CO2 is t

Regioselective Diboron-Mediated Semireduction of Terminal Allenes

A method for the regioselective reduction of the terminal double bond of 1,1-disubstituted allenes has been developed. In the presence of a palladium catalyst, tetrahydroxydiboron and stoichiometric water, allene semireduction proceeds in high yield to afford Z-alkenes selectively.

Asymmetric Nitrone Synthesis via Ligand-Enabled Copper-Catalyzed Cope-Type Hydroamination of Cyclopropene with Oxime

We report realization of the first enantioselective Cope-type hydroamination of oximes for asymmetric nitrone synthesis. The ligand promoted asymmetric cyclopropene "hydronitronylation" process employs a Cu-based catalytic system and readily available starting materials, operates under mild conditions and displays broad scope and exceptionally high enantio- and diastereocontrol. Preliminary mechanistic studies corroborate a CuI-catalytic profile featuring an olefin metalla-retro-Cope aminocupration process as the key C-N bond forming event. This conceptually novel reactivity enables the first example of highly enantioselective catalytic nitrone formation process and will likely spur further developments that may significantly expedite chiral nitrone synthesis.

Iodothiocyanation/Nitration of Allenes with Potassium Thiocyanate/Silver Nitrite and Iodine

Direct strategies for the iodothiocyanation and iodonitration of allenes have been developed. In this process, potassium thiocyanate/silver nitrite and molecular iodine are used as the source of SCN, ONO2and iodine to provide the desired products in moderate to good yields with high stereoselectivity. (Figure presented.).

Preparative resolution of bromocyclopropylcarboxylic acids

A general and efficient method for the preparative resolution of α- and β-bromocyclopropylcarboxylic acids has been developed. This protocol involves a sequence of two crystallizations with pseudo-enantiomeric amines, cinchonine, and cinchonidine, which yield both enantiomers of the acid in highly enriched form. Both alkaloids can be easily recovered and reused multiple times without any loss of efficacy.

Lewis acid promoted reactions of ethenetricarboxylates with allenes: Synthesis of indenes and γ-lactones via conjugate addition/cyclization reaction

(Figure presented) Indenes are important core structures in organic chemistry. Few simple arylallenes have been used to construct indene skeletons by Friedel-Crafts reaction. Lewis acid catalyzed reaction of ethenetricarboxylates 1 and arylallenes has been examined in this study. The reaction of arylallenes and ethenetricarboxylate triesters with SnCl4 gave indene derivatives efficiently, via a conjugate addition/Friedel-Crafts cyclization reaction. On the other hand, the reactions of 1,1-diethyl 2-hydrogen ethenetricarboxylate and arylallenes or alkylallenes with SnCl4 at -78 °C or room temperature and subsequent treatment with Et3N gave γ-lactones. The reactions of triethyl ethenetricarboxylate and 1,1-dialkylallenes with SnCl4 at room temperature also gave γ-lactones.