863310-91-2

Upstream product

• 53484-50-7 (E)-p-methoxy-cinnamyl alcohol 
• 873-55-2 sodium benzenesulfonate 
• 496789-06-1 (E)-p-methoxycinnamyl methyl carbonate 
• 4180-23-8 E-1-(4'-methoxyphenyl)prop-1-ene 
• 80-17-1 benzenesufonyl hydrazide 
• 5703-26-4 4-Methoxyphenylacetaldehyde 
• 56069-39-7 diethyl phenylsulfonylmethylphosphonate 
• 20850-13-9 (E)-3-(4-methoxyphenyl)prop-2-en-1-amine 

Relevant academic research and scientific papers

Palladium-catalyzed substitution of allylic alcohols with sulfinate salts: A synthesis of bicalutamide

A method is presented for the direct substitution of allylic alcohols with sodium arylsulfinates. The process involves a cooperative action of palladium catalysts, phenylboronic acid and titanium tetraisopropoxide. By taking advantage of this protocol, we achieved a concise synthesis of bicalutamide, an anti-androgen compound for treating prostate cancer.

Regioselective Single-Electron Tsuji-Trost Reaction of Allylic Alcohols: A Photoredox/Nickel Dual Catalytic Approach

A radical-mediated functionalization of allyl alcohol derived partners with a variety of alkyl 1,4-dihydropyridines via photoredox/nickel dual catalysis is described. This transformation transpires with high linear and E-selectivity, avoiding the requirement of harsh conditions (e.g., strong base, elevated temperature). Additionally, using aryl sulfinate salts as radical precursors, allyl sulfones can also be obtained. Kinetic isotope effect experiments implicated oxidative addition of the nickel catalyst to the allylic electrophile as the turnover-limiting step, supporting previous computational studies.

Copper-catalyzed aerobic oxidative N-S bond functionalization for C-S bond formation: Regio- and stereoselective synthesis of sulfones and thioethers

A regio- and stereoselective synthesis of sulfones and thioethers by means of CuI-catalyzed aerobic oxidative N-S bond cleavage of sulfonyl hydrazides, followed by cross-coupling reactions with alkenes and aromatic compounds to form the C-sp-2-S bond, is described herein. N2 and H2O are the byproducts of this transformation, thus offering an environmentally benign process with a wide range of potential applications in organic synthesis and medicinal chemistry. First cleave, then cross-couple: A direct Cu-catalyzed aerobic oxidative C-sp-2-H functionalization and C-S bond coupling reaction has been developed (see scheme). By slight modification of the additive, sulfonyl hydrazides could serve as sulfonation, sulfenation, or arylation reagents to undergo cross-coupling reactions with alkenes and (hetero)aromatic cycles, affording sulfones, thioethers, and biaryl compounds with high regio- and stereoselectivities (see scheme).

A base-controlled regioselective synthesis of allyl and vinyl phenyl sulfones

A reaction of diethyl phenylsulfonylmethylphosphonate with 2-arylacetaldehydes in the presence of a catalytic excess of sodium hydride (1.1 equiv) yields allyl phenyl sulfones in excellent yield under mild reaction conditions. In contrast, when less than 1 equiv of sodium hydride (0.90 equiv) is used, the corresponding vinyl phenyl sulfones are obtained exclusively. The vinyl phenyl sulfones can be completely converted to allyl phenyl sulfones with only 0.2 equiv of NaH, suggesting that the second hydride involvement in the above transformation is catalytic. The regioselective control observed in these reactions offers a general method for synthesizing novel vinyl and allyl phenyl sulfones in one step from the same starting materials. The regioselectivity and stereoselectivity of this reaction, however, are not maintained when 2-alkylacetaldehydes are reacted with diethyl phenylsulfonylmethylphosphonate under identical reaction conditions. Our results indicate that an extended conjugation of the double bond in allylsulfones formed from the reaction of 2-arylacetaldehydes is required for the observed regio- and stereoselectivity.

Direct substitution of primary allylic amines with sulfinate salts

The NH2 group in primary allylic amines was substituted directly by sulfinate salts with excellent regio- and stereoselectivities. In the presence of 0.1 mol % [Pd(allyl)Cl]2, 0.4 mol % 1,4- bis(diphenylphosphino)butane (dppb), and excess boric acid, a range of α-unbranched primary allylic amines were smoothly substituted with sodium sulfinates in an α-selective fashion to give structurally diverse allylic sulfones in good to excellent yields with exclusive E selectivity. Replacing dppb with 1,1′-bi-2-naphthol (BINOL) allowed unsymmetric α-chiral primary allylic amines to be transformed into the corresponding allylic sulfones in good to excellent yields with excellent retention of ee. Importantly, the reaction complements known asymmetric methods in substrate scope via its unique ability to provide α-chiral allylic sulfones with high optical purity starting from unsymmetric allylic electrophiles.

π-Allylic sulfonylation in water with amphiphilic resin-supported palladium-phosphine complexes

π-Allylic substitution of allyl esters with sodium arylsul-finate was performed with an amphiphilic polystyrene-poly(ethylene glycol) (PS-PEG) resin-supported phosphine-palladium complex in water as a single reaction medium under heterogeneous conditions to give allyl sulfones in good to high yields. Catalytic asymmetric allylic substitution of cycloalkenyl esters also took place in water using a PS-PEG resin-supported chiral imidazo-indolephosphine- palladium complex to give cycloalkenyl sulfones with up to 81% ee.

Palladium-triethylborane-triggered direct and regioselective conversion of allylic alcohols to allyl phenyl sulfones?

A combination of Pd(OAc)2 (5 mol %), PPh3 (10 mol %), and Et3B (200 mol %) promotes the formation of allyl phenyl sulfones from the allylic alcohols directly with excellent yields under mild conditions. The activation of an alcohol group is not necessary which is achieved in situ. The conjugated dienols also were equally effective for the said transformation.