Monofunctionalization of Symmetric Difunctional Substrates

Dörwald, Florencio Zaragoza

doi:10.1002/352760426x.ch10

Side Reactions in Organic Synthesis 2004

DOI: 10.1002/352760426x.ch10

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Monofunctionalization of Symmetric Difunctional Substrates

Florencio Zaragoza Dörwald

Abstract: 336 Scheme 10.3. Microorganism-mediated hydrolysis of dinitriles and diamides [9]. Scheme 10.4. Acetylation of meso-hydrobenzoin [11]. 10.3 Monofunctionalization of Diols Scheme 10.22. Nucleophilic substitutions at symmetric 1,2-dihaloethanes [93, 94].

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Cited by 4 publications

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Cavitands as Reaction Vessels and Blocking Groups for Selective Reactions in Water

et al. 2016

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The majority of reactions currently performed in the chemical industry take place in organic solvents,c ompounds that are generally derived from petrochemicals.T op romote chemical processes in water,weexamined the use of synthetic, deep water-soluble cavitands in the Staudinger reduction of long-chain aliphatic diazides (C 8 ,C 10 ,a nd C 12 ). The diazide substrates are taken up by the cavitand in D 2 Oi nf olded, dynamic conformations.T he reduction of one azide group to an amine gives acomplex in which the substrate is fixedinan unsymmetrical conformation, with the amine terminal exposed and the azide terminal deep and inaccessible within the cavitand. Accordingly,t he reduction of the second azide group is inhibited, even with excess phosphine,and good yields of the monofunctionalized products are obtained. In contrast, the reduction of the free diazides in bulk solution yields diamine products.Supportinginformation (synthesis and characterization of new compounds,materials, methods for all experiments, kinetic modeling details, and additional spectral data) and the ORCID identification number(s) for the author(s) of this article can be found under http://dx.

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Cavitands as Reaction Vessels and Blocking Groups for Selective Reactions in Water

et al. 2016

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show abstract

Cavitands as Reaction Vessels and Blocking Groups for Selective Reactions in Water

et al. 2016

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The majority of reactions currently performed in the chemical industry take place in organic solvents, compounds that are generally derived from petrochemicals. To promote chemical processes in water, we examined the use of synthetic, deep water-soluble cavitands in the Staudinger reduction of long-chain aliphatic diazides (C8 , C10 , and C12 ). The diazide substrates are taken up by the cavitand in D2 O in folded, dynamic conformations. The reduction of one azide group to an amine gives a complex in which the substrate is fixed in an unsymmetrical conformation, with the amine terminal exposed and the azide terminal deep and inaccessible within the cavitand. Accordingly, the reduction of the second azide group is inhibited, even with excess phosphine, and good yields of the monofunctionalized products are obtained. In contrast, the reduction of the free diazides in bulk solution yields diamine products.

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Silica‐Mediated Monohydrolysis of Dicarboxylic Esters

Dyker

2021

Eur J Org Chem

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A new method for the monohydrolysis of dicarboxylic esters is presented, involving as key step a silanolysis at elevated temperatures at the silica gel surface. In the second step, the surface bound silyl esters are cleaved off under mild conditions, giving a straightforward and fast access to half esters. Based on recovered starting material generally yields well above 70 % are achieved, both, with stiff aromatic as well as flexible aliphatic substrates, as long as the ester groups involved are remote enough from each other. Otherwise competing reactions are becoming determinative, anhydride formation in the case of phthalates and decarbonylative fragmentation in the case of malonates. The new method was also successfully tested on a multigram scale with a minimalistic apparatus setup.

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Monofunctionalization of Symmetric Difunctional Substrates

Abstract: 336 Scheme 10.3. Microorganism-mediated hydrolysis of dinitriles and diamides [9]. Scheme 10.4. Acetylation of meso-hydrobenzoin [11]. 10.3 Monofunctionalization of Diols Scheme 10.22. Nucleophilic substitutions at symmetric 1,2-dihaloethanes [93, 94].

Cited by 4 publications

References 54 publications

Cavitands as Reaction Vessels and Blocking Groups for Selective Reactions in Water

Cavitands as Reaction Vessels and Blocking Groups for Selective Reactions in Water

Cavitands as Reaction Vessels and Blocking Groups for Selective Reactions in Water

Silica‐Mediated Monohydrolysis of Dicarboxylic Esters

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