42337-03-1

Upstream product

• 120-57-0 piperonal 
• 107-05-1 3-chloroprop-1-ene 
• 1730-25-2 allylmagnesium bromide 
• 107-18-6 allyl alcohol 
• 106-95-6 allyl bromide 
• 591-87-7 Allyl acetate 
• 191732-48-6 (E)-(3-bromoprop-1-en-1-yl)tributylstannane 
• 24850-33-7 allyltributylstanane 
• 556-56-9 allyl iodid 

Downstream Products

• 120-57-0 piperonal 
• 5420-97-3 1-acetoxy-1-(3',4'-methylenedioxyphenyl)but-3-ene 
• 406486-91-7 4β-acetoxy-2β,6β-diethyl-tetrahydropyran 
• 1242077-06-0 (E)-1-(4-(benzo[d][1,3]dioxol-5-yl)but-3-en-2-yl)-4-phenyl-1H-1,2,3-triazole 
• 143503-94-0 rac-1-(benzo[d][1,3]dioxol-5-yl)-4-(3,4,5-trimethoxyphenyl)butan-1-ol 
• 56438-69-8 rac-1-(benzo[d][1,3]dioxol-5-yl)-4-(3,4,5-trimethoxyphenyl)butan-1-one 
• 63814-03-9 1,2,3,3a,4,5,12b,12c-octahydro-7H-1,3-benzodioxolo[5,6-c]pyrrolo[3,2,1-ij]quinoline 
• 1449790-07-1 3-(1,3-benzodioxol-5-yl)-6-(2-bromophenyl)hex-1-en-3-ol 
• 1449790-06-0 2-(1,3-benzodioxol-5-yl)-5-(2-bromophenyl)pentan-2-ol 
• 1449790-03-7 1-(1,3-benzodioxol-5-yl)-4-(2-bromo-5-methoxyphenyl)butan-1-ol 
• 1449789-97-2 1-(1,3-benzodioxol-5-yl)-4-(2-bromophenyl)butan-1-ol 
• 1449789-93-8 1-(1,3-benzodioxol-5-yl)-4-(2-bromo-5-methoxyphenyl)butan-1-one 

Relevant academic research and scientific papers

Photoredox Allylation Reactions Mediated by Bismuth in Aqueous Conditions

Organometallic allylic reagents are widely used in the construction of C?C bonds by Barbier-type reactions. In this communication, we have described a photoredox Barbier allylation of aldehydes mediated by bismuth, in absence of other metals as co-reductants. Mild reaction conditions, tolerance of oxygen, and use of aqueous solvent make this photoredox methodology attractive for green and sustainable synthesis of homoallylic alcohols.

A total synthesis of racemic paulownin using a type II photocyclization reaction

The lignan paulownin was prepared in a seven-step route from piperonal. The key step was a type II photocyclization reaction wherein two of the four stereogenic centers were introduced.

Catalytic Photoredox Allylation of Aldehydes Promoted by a Cobalt Complex

The preparation of homoallylic alcohols by addition of organometallic allyl compounds to carbonyls is an important strategy in organic chemistry. Allylating organometallic cobalt species can be generated employing stoichiometric quantities of Zn acting as reductant. To avoid the employment of stoichiometric amount of Zn, we have developed an allylation reaction of aromatic and aliphatic aldehydes promoted by photoredox catalysis in the presence of a cobalt complex, and we present herein a full account of our research. In the presence of the abundant CoBr2 (10 mol %), 4,4′-di-tert-butyl-2,2′-dipyridyl (dtbbpy, 10 mol %), allyl acetate (3 equiv.), [Ir(dtbbpy)(ppy)2]PF6 (ppy=2-phenylpyridine, 2 mol %), and N,N-diisopropylethylamine (4 equiv.), an allylation of aldehydes is taking place, in moderate to good yields. Substrates scope, limitations, and photophysical investigations of this new process are reported. (Figure presented.).

Photocatalytic Umpolung Synthesis of Nucleophilic π-Allylcobalt Complexes for Allylation of Aldehydes

The concept of "umpolung"reactivity of π-allylmetal complexes has been developed as a powerful method for the allylation of aldehydes. This paper describes the photocatalytic umpolung strategy for the synthesis of nucleophilic allylcobalt complexes through a single-electron-transfer (SET) process. This strategy enables the metallaphotoredox allylation of carbonyls with allyl acetate using organic N,N-diisopropylethylamine as the terminal reductant bypassing the use of a stoichiometric amount of metals. Ultraviolet-visible spectroscopy was used to monitor the redox changes of cobalt in the reaction.

Cu-catalyzed hydroxycyclopropanol ring-opening cyclization to tetrahydrofurans and tetrahydropyrans: short total syntheses of hyperiones

Tetrahydrofurans (THFs) and tetrahydropyrans (THPs) are important core scaffolds frequently found in many molecules of medicinal importance. Herein, we report a novel copper-catalyzed hydroxycyclopropanol ring-opening cyclization methodology to synthesize di- or tri-substituted THFs and THPs. In this reaction, a strained C-C bond was cleaved and a new Csp3-O bond was formed to produce the aforementioned O-heterocycles. The new THF synthesis features a broad substrate scope, scalability, and good functional-group tolerability. It enabled us to complete the shortest enantioselective syntheses of hyperiones A and B (3 and 4 steps, respectively), which is significantly shorter than the previously reported two total syntheses (≥10 steps).

Cp2TiCl2-Catalyzed Photoredox Allylation of Aldehydes with Visible Light

A Barbier-type Cp2TiCl2-mediated (10 mol %) photoredox allylation of aldehydes under irradiation with visible light (blue light-emitting diodes (LEDs), 450 nm) and in the presence of an organic dye (3DPAFIPN, 5 mol %) with allylbromides is described.

Nickel-Catalyzed Hydroarylation of in Situ Generated 1,3-Dienes with Arylboronic Acids Using a Secondary Homoallyl Carbonate as a Surrogate for the 1,3-Diene and Hydride Source

The nickel-catalyzed hydroarylation of 1,3-dienes with arylboronic acids using a secondary homoallyl carbonate as a surrogate for the 1,3-diene and hydride source has been developed. The synthetic strategy allowed an efficient access to a wide array of hydroarylation products in high yields with high functional group compatibility without the use of an external hydride source. Mechanistic experiments indicated that the alkene-directed oxidative addition and subsequent β-hydride elimination would be a critical process in this transformation.

MnO2as a terminal oxidant in Wacker oxidation of homoallyl alcohols and terminal olefins

Efficient and mild reaction conditions for Wacker-type oxidation of terminal olefins of less explored homoallyl alcohols to β-hydroxy-methyl ketones have been developed by using a Pd(ii) catalyst and MnO2 as a co-oxidant. The method involves mild reaction conditions and shows good functional group compatibility along with high regio- and chemoselectivity. While our earlier system of PdCl2/CrO3/HCl produced α,β-unsaturated ketones from homoallyl alcohols, the present method provided orthogonally the β-hydroxy-methyl ketones. No overoxidation or elimination of benzylic and/or β-hydroxy groups was observed. The method could be extended to the oxidation of simple terminal olefins as well, to methyl ketones, displaying its versatility. An application to the regioselective synthesis of gingerol is demonstrated.

Allylation of aldehydes by dual photoredox and nickel catalysis

Here we report the application of dual nickel/photoredox catalysis to the allylation of aliphatic, aromatic and heteroaromatic aldehydes by using commercially available reagents. The process utilizes the combination of a Ni(ii) complex, [Ru(bpy)3]2+ as a photoredox catalyst, and allylacetate under blue LED irradiation, and allows the synthesis of a large variety of homoallylic alcohols.

Chemoenzymatic Total Synthesis of Deoxy-, epi-, and Podophyllotoxin and a Biocatalytic Kinetic Resolution of Dibenzylbutyrolactones

Podophyllotoxin is probably the most prominent representative of lignan natural products. Deoxy-, epi-, and podophyllotoxin, which are all precursors to frequently used chemotherapeutic agents, were prepared by a stereodivergent biotransformation and a biocatalytic kinetic resolution of the corresponding dibenzylbutyrolactones with the same 2-oxoglutarate-dependent dioxygenase. The reaction can be conducted on 2 g scale, and the enzyme allows tailoring of the initial, “natural” structure and thus transforms various non-natural derivatives. Depending on the substitution pattern, the enzyme performs an oxidative C?C bond formation by C?H activation or hydroxylation at the benzylic position prone to ring closure.