A Practical and General Approach to the Late-Stage Functionalization of Complex Sulfonamides

2019 ◽  
Author(s):  
Patrick Fier ◽  
Kevin M. Maloney
Keyword(s):  
Functional Groups ◽  
Late Stage ◽  
Building Blocks ◽  
Pharmaceutical Compounds ◽  
Stage Conversion

Herein we describe the development and application of a method for the mild, late-stage conversion of primary sulfonamides to several other other functional groups. These reactions occur via initial reductive deamination of sulfonamides to sulfinates via an NHC-catalyzed reaction of transiently formed <i>N</i>-sulfonylimines. The method described here is tolerant of nearly all common functional groups, as exemplified by the late-stage derivatization of several complex pharmaceutical compounds. Based on the prevalence of sulfonamide-containing drugs and building blocks, we have developed a method to enable sulfonamides to be applied as versatile synthetic handles for synthetic chemsitry.

A Practical and General Approach to the Late-Stage Functionalization of Complex Sulfonamides

2019 ◽  
Author(s):  
Patrick Fier ◽  
Kevin M. Maloney
Keyword(s):  
Functional Groups ◽  
Late Stage ◽  
Building Blocks ◽  
Pharmaceutical Compounds ◽  
Stage Conversion

Herein we describe the development and application of a method for the mild, late-stage conversion of primary sulfonamides to several other other functional groups. These reactions occur via initial reductive deamination of sulfonamides to sulfinates via an NHC-catalyzed reaction of transiently formed <i>N</i>-sulfonylimines. The method described here is tolerant of nearly all common functional groups, as exemplified by the late-stage derivatization of several complex pharmaceutical compounds. Based on the prevalence of sulfonamide-containing drugs and building blocks, we have developed a method to enable sulfonamides to be applied as versatile synthetic handles for synthetic chemsitry.

scholarly journals Facile Synthesis of Sulfonyl Chlorides/Bromides from Sulfonyl Hydrazides

2021 ◽  
Author(s):  
Rongxiang Chen ◽  
Shaohong Xu ◽  
Fumin Shen ◽  
Canran Xu ◽  
Kai-Kai Wang ◽  
...  
Keyword(s):  
Functional Groups ◽  
Rapid Method ◽  
Late Stage ◽  
Efficient Synthesis ◽  
Facile Synthesis ◽  
Sulfonyl Chlorides ◽  
Stage Conversion

A simple and rapid method for efficient synthesis of sulfonyl chlorides/bromides from sulfonyl hydrazide with NXS (X = Cl or Br) and late-stage conversion to several other functional groups has been described. A variety of nucleophiles could be engaged in this transformation thus permitting the synthesis of complex sulfonamides, sulfonates. In most cases, these reactions are highly selective, simple, and clean, affording products in excellent yields.

scholarly journals Facile Synthesis of Sulfonyl Chlorides/Bromides from Sulfonyl Hydrazides

Molecules ◽  
2021 ◽  
Vol 26 (18) ◽  
pp. 5551
Author(s):  
Rongxiang Chen ◽  
Shaohong Xu ◽  
Fumin Shen ◽  
Canran Xu ◽  
Kaikai Wang ◽  
...  
Keyword(s):  
Functional Groups ◽  
Rapid Method ◽  
Late Stage ◽  
Efficient Synthesis ◽  
Facile Synthesis ◽  
Sulfonyl Chlorides ◽  
Stage Conversion

A simple and rapid method for efficient synthesis of sulfonyl chlorides/bromides from sulfonyl hydrazide with NXS (X = Cl or Br) and late-stage conversion to several other functional groups was described. A variety of nucleophiles could be engaged in this transformation, thus permitting the synthesis of complex sulfonamides and sulfonates. In most cases, these reactions are highly selective, simple, and clean, affording products at excellent yields.

Reductive Cleavage of Secondary Sulfonamides: Converting Terminal Functional Groups into Versatile Synthetic Handles

2019 ◽  
Author(s):  
Patrick Fier ◽  
Suhong Kim ◽  
Kevin M. Maloney
Keyword(s):  
Functional Groups ◽  
Late Stage ◽  
Reductive Cleavage ◽  
Bioactive Molecules ◽  
General Method

Sulfonamides are pervasive in drugs and agrochemicals, yet are typically considered as terminal functional groups rather than synthetic handles. To enable the general late-stage functionalization of secondary sulfonamides, we have developed a mild and general method to reductively cleave the N-S bonds of sulfonamides to generate sulfinates and amines, components which can further react <i>in-situ</i> to access a variety of other medicinally relevant functional groups. The utility of this platform is highlighted by the selective manipulation of several complex bioactive molecules.

scholarly journals Non-Enzymatic Desymmetrization Reactions in Aqueous Media

Symmetry ◽  
2021 ◽  
Vol 13 (4) ◽  
pp. 720
Author(s):  
Satomi Niwayama
Keyword(s):  
Natural Products ◽  
Total Synthesis ◽  
Functional Groups ◽  
Organic Compounds ◽  
Recent Progress ◽  
Aqueous Media ◽  
Building Blocks ◽  
Organic Reactions ◽  
Environmentally Benign ◽  
Enzymatic Desymmetrization

Symmetric organic compounds are generally obtained inexpensively, and therefore they can be attractive building blocks for the total synthesis of various pharmaceuticals and natural products. The drawback is that discriminating the identical functional groups in the symmetric compounds is difficult. Water is the most environmentally benign and inexpensive solvent. However, successful organic reactions in water are rather limited due to the hydrophobicity of organic compounds in general. Therefore, desymmetrization reactions in aqueous media are expected to offer versatile strategies for the synthesis of a variety of significant organic compounds. This review focuses on the recent progress of desymmetrization reactions of symmetric organic compounds in aqueous media without utilizing enzymes.

scholarly journals Combined Photoredox and Carbene Catalysis for the Synthesis of Ketones from Carboxylic Acids

2020 ◽  
Author(s):  
Anna Davies ◽  
keegan fitzpatrick ◽  
Rick Betori ◽  
Karl Scheidt
Keyword(s):  
Carboxylic Acids ◽  
Late Stage ◽  
Pharmaceutical Compounds ◽  
Single Electron ◽  
Photoredox Catalysis ◽  
Radical Coupling ◽  
Electron Reduction

Disclosed herein is the development of a novel single-electron reduction of acyl azoliums for the formation of ketones from carboxylic acids. Facile construction of the acyl azolium <i>in situ</i> followed by a radical-radical coupling was made possible using merged NHC-photoredox catalysis. The utility of this protocol in synthesis was demonstrated in the late-stage functionalization of a variety of pharmaceutical compounds.

scholarly journals A Single-Step Synthesis of Azetidine-3-Amines

2020 ◽  
Author(s):  
Brian J Wang ◽  
Matthew Duncton
Keyword(s):  
Functional Groups ◽  
Late Stage ◽  
Single Step ◽  
Secondary Amines ◽  
High Yield ◽  
Primary Amines ◽  
Privileged Structure ◽  
One Step ◽  
Alternative Procedures ◽  
Approved Drugs

<div> <p>The azetidine group is frequently encountered within contemporary medicinal chemistry where it is viewed as a privileged structure. However, the introduction of an azetidine can be synthetically challenging. Herein, a straight-forward one step synthesis of azetidine-3-amines, starting from a bench stable, commercial material is presented. The reaction tolerates functional groups commonly encountered in biological-, medicinal- and agro-chemistry, and proceeds in moderate-to-high yield with secondary amines, and moderate-to-low yield with primary amines. The methodology compares favorably to recent alternative procedures and can be utilized in “any-stage” functionalization, including late-stage azetidinylation of approved drugs and other compounds with pharmacological activity.</p> </div>

scholarly journals Self assembled nanocages from DNA–protoporphyrin hybrid molecules

RSC Advances ◽  
2015 ◽  
Vol 5 (108) ◽  
pp. 89025-89029 ◽  
Author(s):  
Vandana Singh ◽  
Mohan Monisha ◽  
Roy Anindya ◽  
Prolay Das
Keyword(s):  
Functional Groups ◽  
Protoporphyrin Ix ◽  
Building Blocks ◽  
Carboxyl Groups ◽  
Dna Oligomers ◽  
Organic Hybrid ◽  
Molecular Building Blocks ◽  
Modified Dna ◽  
Hybrid Molecules ◽  
Self Assembled

DNA–organic hybrid molecular building blocks are generated by covalent conjugation of the carboxyl groups of protoporphyrin IX with the amine functional groups of modified DNA oligomers.

The dual reactivity of Weinreb amides applied to the late-stage divergent functionalisation of meso pyrrolidines

2018 ◽  
Vol 42 (15) ◽  
pp. 12403-12411 ◽  
Author(s):  
Hamza Boufroura ◽  
Laurent Sevaille ◽  
Nicolas Gigant ◽  
Emmanuelle Drège ◽  
Delphine Joseph
Keyword(s):  
Late Stage ◽  
Building Blocks ◽  
Dual Reactivity ◽  
Weinreb Amides

The dual reactivity of Weinreb amides was exploited to prepare diversified symmetrical and dissymmetrical 2,5-disubstituted pyrrolidines from simple building blocks.

A Chiral Interlocking Auxiliary Strategy for the Synthesis of Mechanically Planar Chiral Rotaxanes

2021 ◽  
Author(s):  
Alberto de Juan ◽  
David Lozano ◽  
Andrew Heard ◽  
Michael Jinks ◽  
Jorge Meijide Suarez ◽  
...  
Keyword(s):  
Functional Groups ◽  
Direct Synthesis ◽  
Building Blocks ◽  
Bond Forming ◽  
Single Target

We have serendipitously discovered a combination of reaction partners that function as a “chiral interlocking auxiliary” to both orientate a macrocycle and, effectively, load it onto a new axle. We demonstrate the potential of this finding through the synthesis of a number of targets in high enantiopurity, without separation of stereoisomers, including examples whose axles lack any functional groups that would allow their direct synthesis by other means, so called “impossible” rotaxanes. Intriguingly, by varying the order of bond forming steps, we can effectively choose which end of an axle the macrocycle is loaded onto, allowing the synthesis of both hands of a single target using the same reactions and building blocks.

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