20879-06-5

Upstream product

• 6054-00-8 3-phenyl-2H-benzopyran 
• 78950-74-0 2-morpholinoisoflav-3-ene 
• 100976-02-1 2-phenyl-3-(2-hydroxyphenyl)-1-propanol 
• 90-01-7 salicylic alcohol 
• 109790-47-8 2-(o-hydroxymethylphenoxy)-1-phenylethanone 
• 109790-41-2 [2-(2-oxo-2-phenylethoxy)benzyl]triphenylphosphonium bromide 
• 70-11-1 α-bromoacetophenone 
• 254-04-6 2H-chromene 
• 98-80-6 phenylboronic acid 
• 109790-37-6 6-chloro-3-(4-chlorophenyl)-2H-benzopyran 
• 33255-30-0 3-phenyl-2,3,4,5-tetrahydro-benzo[f][1,4]oxazepine 
• 37434-59-6 dimethyl 2-phenylmalonate 
• 591-50-4 iodobenzene 
• 122-78-1 phenylacetaldehyde 

Relevant academic research and scientific papers

Skeletal editing through direct nitrogen deletion of secondary amines

Synthetic chemistry aims to build up molecular complexity from simple feedstocks1. However, the ability to exert precise changes that manipulate the connectivity of the molecular skeleton itself remains limited, despite possessing substantial potential to expand the accessible chemical space2,3. Here we report a reaction that ‘deletes’ nitrogen from organic molecules. We show that N-pivaloyloxy-N-alkoxyamides, a subclass of anomeric amides, promote the intermolecular activation of secondary aliphatic amines to yield intramolecular carbon–carbon coupling products. Mechanistic experiments indicate that the reactions proceed via isodiazene intermediates that extrude the nitrogen atom as dinitrogen, producing short-lived diradicals that rapidly couple to form the new carbon–carbon bond. The reaction shows broad functional-group tolerance, which enables the translation of routine amine synthesis protocols into a strategy for carbon–carbon bond constructions and ring syntheses. This is highlighted by the use of this reaction in the syntheses and skeletal editing of bioactive compounds.

A concise route towards isoflavans

Isoflavans have gained considerable interest owing to their potential health benefits. Herein, we have presented a straightforward strategy for isoflavans synthesis. The strategy features an intermolecular [Cu]-catalyzed arylation of malonates and an intr

Iridium-Catalyzed Enantioselective Hydrogenation of Indole and Benzofuran Derivatives

Enantioselective hydrogenation of a broad spectrum of N-, O-, and S-containing aromatic benzoheterocycles or nonaromatic unsaturated heterocycles has been realized by using an Ir/SpinPHOX (SpinPHOX=spiro[4,4]-1,6-nonadiene-based phosphine-oxazoline) complex as the catalyst, affording an array of the corresponding chiral benzoheterocycles (30 examples) with excellent enantioselectivities (>99 % ee in most cases) and turnover numbers up to 500.

Rhodium-catalyzed asymmetric addition of arylboronic acids to 2: H-chromenes leading to 3-arylchromane derivatives

Asymmetric addition of arylboronic acids to 2H-chromenes proceeded in the presence of a hydroxorhodium/chiral diene catalyst to give 3-arylchromanes in high yields with high enantioselectivity. The reaction involves 1,4-Rh shift before protonation to release the addition product and to regenerate the hydroxorhodium species.

Iridium-Catalyzed Asymmetric Hydrogenation of 2H-Chromenes: A Highly Enantioselective Approach to Isoflavan Derivatives

A highly efficient (aS)-Ir/In-BiphPHOX-catalyzed asymmetric hydrogenation of substituted 2H-chromenes and substituted benzo[e][1,2]oxathiine 2,2-dioxides is described. A series of 2H-chromenes and benzo[e][1,2]oxathiine 2,2-dioxides were hydrogenated to give the target products in high yields (92-99%) with excellent enantioselectivities (up to 99.7% ee) using our catalytic system. This reaction provides a direct and efficient method for the construction of chiral benzo six-membered oxygen-containing compounds.

2-Morpholinoisoflav-3-enes as flexible intermediates in the synthesis of phenoxodiol, isophenoxodiol, equol and analogues: Vasorelaxant properties, estrogen receptor binding and Rho/RhoA kinase pathway inhibition

Isoflavone consumption correlates with reduced rates of cardiovascular disease. Epidemiological studies and clinical data provide evidence that isoflavone metabolites, such as the isoflavan equol, contribute to these beneficial effects. In this study we developed a new route to isoflavans and isoflavenes via 2-morpholinoisoflavenes derived from a condensation reaction of phenylacetaldehydes, salicylaldehydes and morpholine. We report the synthesis of the isoflavans equol and deoxygenated analogues, and the isoflavenes 7,4′-dihydroxyisoflav-3-ene (phenoxodiol, haganin E) and 7,4′-dihydroxyisoflav-2-ene (isophenoxodiol). Vascular pharmacology studies reveal that all oxygenated isoflavans and isoflavenes can attenuate phenylephrine-induced vasoconstriction, which was unaffected by the estrogen receptor antagonist ICI 182,780. Furthermore, the compounds inhibited U46619 (a thromboxane A2 analogue) induced vasoconstriction in endothelium-denuded rat aortae, and reduced the formation of GTP RhoA, with the effects being greatest for equol and phenoxodiol. Ligand displacement studies of rat uterine cytosol estrogen receptor revealed the compounds to be generally weak binders. These data are consistent with the vasorelaxation activity of equol and phenoxodiol deriving at least in part by inhibition of the RhoA/Rho-kinase pathway, and along with the limited estrogen receptor affinity supports a role for equol and phenoxodiol as useful agents for maintaining cardiovascular function with limited estrogenic effects.

o-Quinone methide based approach to isoflavans: application to the total syntheses of equol, 3′-hydroxyequol and vestitol

A concise strategy is developed for the synthesis of isoflavans employing a Diels-Alder reaction between o-quinone methides and aryl-substituted enol ethers followed by reductive cleavage of the acetal group. The method is extended towards the total syntheses of equol, 3′-hydroxyequol and vestitol.

The direct synthesis of isoflavans VIA α-alkylation of phenylacetates

Deprotonation of oxygenated phenylacetates and quenching of the enolates with oxygenated benzylic electrophiles, afforded 2,3-diarylpropanoates which served as precursors to the isoflavans following consecutive reduction and cyclization steps.

A new route to 3,4-dihydro-2H-1-benzopyrans substituted at 3-position via palladium-catalysed reactions

3,4-Dihydro-2H-1-benzopyrans substituted at 3-position were prepared via palladium-catalysed reactions between a triflate and several coupling reagnets (alkyl or aryl tin reagents and borane derivatives) according to Stille or Suzuki methodologies.

The First Enantioselective Synthesis of Isoflavanoids: (R)- and (S)-Isoflavans

α-Benzylation of (+)- and (-)-N-phenylacetyl imidazolidinones with 2-O-methoxymethylbenzyl bromide, followed by reductive removal of the chiral auxiliary and cyclization, leads to isoflavans in excellent enantiomeric excess and yield.