58870-24-9

Upstream product

• 349485-64-9 2-(2-methoxy-benzylidene)amino-benzo[de]isoquinolin-1,3-dione 
• 90-02-8 salicylaldehyde 
• 135-02-4 ortho-anisaldehyde 

Downstream Products

• 40092-39-5 C₁₂H₁₇N₃O₂ 
• 17745-81-2 1,2-bis(2-methoxybenzylidene)hydrazine 
• 2719-71-3 2-methoxy-benzaldehyde pyridin-2-ylhydrazone 
• 883-90-9 o-benzyl anisole 
• 56772-78-2 1-(2,2-dichlorovinyl)-2-methoxybenzene 

Relevant academic research and scientific papers

Addition reactions of organic carbanion equivalents via hydrazones in water

The addition of organometallic reagents to unsaturated bonds is one of the most powerful tools for carbon–carbon bond formations. Alkylation through organometallic reagents requires stoichiometric quantity of metal and tedious anhydrous operation in most cases. Here, we report “umpolung” nucleophilic additions of hydrazones to Michael acceptors, carbonyls and imines in water. Under the catalysis of ruthenium(II), the addition reactions could be carried out in pure water to provide various alkylation products in moderate to good yields.

N-Amino-1,8-Naphthalimide is a Regenerated Protecting Group for Selective Synthesis of Mono-N-Substituted Hydrazines and Hydrazides

A new route to synthesis of various mono-N-substituted hydrazines and hydrazides by involving in a new C?N bond formation by using N-amino-1,8-naphthalimide as a regenerated precursor was invented. Aniline and phenylhydrazines are reproduced upon reacting these individually with 1,8-naphthalic anhydride followed by hydrazinolysis. The practicality and simplicity of this C?N dihalo alkanes; developed a synthon for bond formation protocol was exemplified to various hydrazines and hydrazides. N-amino-1,8-naphthalimide is suitable synthon for transformation for selective formation of mono-substituted hydrazine and hydrazide derivatives. Those are selective mono-amidation of hydrazine with acid halides; mono-N-substituted hydrazones from aldehydes; synthesis of N-aminoazacycloalkanes from acetohydrazide scaffold and inserted to hydroxy derivatives; distinct synthesis of N,N-dibenzylhydrazines and N-benzylhydrazines from benzyl halides; synthesis of N-amino-amino acids from α-halo esters. Ecofriendly reagent N-amino-1,8-naphthalimide was regenerated with good yields by the hydrazinolysis in all procedures.

Switch in Selectivity for Formal Hydroalkylation of 1,3-Dienes and Enynes with Simple Hydrazones

Controlling reaction selectivity is a permanent pursuit for chemists. Regioselective catalysis, which exploits and/or overcomes innate steric and electronic bias to deliver diverse regio-enriched products from the same starting materials, represents a powerful tool for divergent synthesis. Recently, the 1,2-Markovnikov hydroalkylation of 1,3-dienes with simple hydrazones was reported to generate branched allylic compounds when a nickel catalyst was used. As part of the effort, shown here is that a complete switch of Markovnikov to anti-Markovnikov addition is obtained by changing to a ruthenium catalyst, thus providing direct and efficient access to homoallylic products exclusively. Isotopic substitution experiments indicate that no reversible hydro-metallation across the metal-π-allyl system occurred under ruthenium catalysis. Moreover, this protocol is applicable to the regiospecific hydroalkylation of the distal C=C bond of 1,3-enynes.

Efficient Multigram Approach to Acetylenes and CF3-ynones Starting from Dichloroalkenes Prepared by Catalytic Olefination Reaction (COR)

A novel approach to terminal acetylenes based on catalytic olefination reaction COR of arylaldehydes to form dichloroalkenes followed by treatment with nBuLi was elaborated. This method is atom economical and displays high yields and effectivity. The corresponding alkynes can be prepared in up to 97 % yield. One pot procedure towards CF3-ynones was elaborated to provide these products in up to 87 % yield starting from dichloroalkenes.

Palladium-Catalyzed Formal Hydroalkylation of Aryl-Substituted Alkynes with Hydrazones

We have developed an unprecedented Pd-catalyzed formal hydroalkylation of alkynes with hydrazones, which are generated in situ from naturally abundant aldehydes, as both alkylation reagents and hydrogen donors. The hydroalkylation proceeds with high regio- and stereoselectivity to form (Z)-alkenes, which are more difficult to generate compared to (E)-alkenes. The reaction is compatible with a wide range of functional groups, including hydroxy, ester, ketone, nitrile, boronic ester, amine, and halide groups. Furthermore, late-stage modifications of natural products and pharmaceutical derivatives exemplify its unique chemoselectivity, regioselectivity, and synthetic applicability. Mechanistic studies indicate the possible involvement of Pd-hydride intermediates.

Nickel-catalyzed alkyl-alkyl cross-coupling reactions of non-activated secondary alkyl bromides with aldehydes as alkyl carbanion equivalents

A novel nickel-catalyzed alkyl-alkyl cross coupling of non-activated secondary alkyl bromides with aldehydes via hydrazone intermediates has been developed. Aldehydes as alkyl carbanion equivalents replace traditional organometallic reagents. This coupling occurs on the carbon of the hydrazone rather than the nitrogen. In addition, non-activated primary and tertiary alkyl bromides also undergo the cross-coupling reaction to form new C(sp3)-C(sp3) bonds in moderate yields.

Nickel-Catalyzed Regioselective Hydrobenzylation of 1,3-Dienes with Hydrazones

Hydroalkylation of unsaturated hydrocarbons with unstabilized carbon nucleophiles is difficult and remains a major challenge. The disclosed examples so far have mainly focused on the involvement of heteroatom and/or stabilized carbon nucleophiles as efficient reaction partners. Reported here is an unprecedented regioselective nickel-catalyzed hydrobenzylation of 1,3-dienes with hydrazones, generated in situ from abundant aryl aldehydes and ketones and acting as both the sources of unstabilized carbanion equivalent and hydride. With this strategy, both terminal and sterically hindered internal dienes are hydroalkylated efficiently in a highly selective manner, thus providing a reliable catalytic method to construct challenging C(sp3)-C(sp3) bonds.

Nickel-catalyzed cross-coupling of aldehydes with aryl halides: Via hydrazone intermediates

Traditional cross-couplings require stoichiometric organometallic reagents. A novel nickel-catalyzed cross-coupling reaction between aldehydes and aryl halides via hydrazone intermediates has been developed, merging the Wolff-Kishner reduction and the classical cross-coupling reactions. Aromatic aldehydes, aryl iodides and aryl bromides are especially effective in this new cross-coupling chemistry.

Cross-Coupling of Phenol Derivatives with Umpolung Aldehydes Catalyzed by Nickel

A nickel-catalyzed cross-coupling to construct the C(sp2)-C(sp3) bond was developed from two sustainable biomass-based feedstocks: phenol derivatives with umpolung aldehydes. This strategy features the in situ generation of moisture/air-stable hydrazones from naturally abundant aldehydes, which act as alkyl nucleophiles under catalysis to couple with readily available phenol derivatives. The avoidance of using both halides as the electrophiles and organometallic or organoboron reagents (also derived from halides) as the nucleophiles makes this method more sustainable. Water tolerance, great functional group (ketone, ester, free amine, amide, etc.) compatibility, and late-stage elaboration of complex biological molecules exemplified its practicability and unique chemoselectivity over organometallic reagents.

A naphthalimide-based solid state luminescent probe for ratiometric detection of aluminum ions:: In vitro and in vivo applications

A naphthalimide-based fluorescent probe 4 has been designed and synthesized that detects Al3+ ions in solution, solid state and in biological systems, including cells, tissues and nematodes. Further, a portable kit has been developed using probe 4 for the on-site detection of Al3+ ions.