Sulfonyl Azides Research Articles

Front Cover Picture: Sequential Functionalization of the OH and C(sp2)O Bonds of Tropolones by Alkynes and N‐Sulfonyl Azides (Adv. Synth. Catal. 7/2016)

Front Cover Picture: Sequential Functionalization of the OH and C(<i>sp</i>²)O Bonds of Tropolones by Alkynes and <i>N</i>‐Sulfonyl Azides (Adv. Synth. Catal. 7/2016)

Sequential Functionalization of the OH and C(sp2)O Bonds of Tropolones by Alkynes and N‐Sulfonyl Azides

AbstractSequential copper‐catalyzed [3+2] cycloaddition, rhodium‐catalyzed OH insertion, intramolecular 1,8‐addition, and rearrangement starting from 1‐alkynes, N‐sulfonyl azides, and tropolones is demonstrated for the synthesis of the 2‐functionalized aminotropones in one pot. These results indicate that sequential functionalization of OH and C(sp2)O bonds smoothly occurs in the C(sp2)OH bonds of tropolonemagnified image

Transition-Metal-Free Oxidative Aliphatic C-H Azidation.

The first example of a practical and selective azidation of unactivated aliphatic C-H bonds with easily handled sulfonyl azides as azide source without the use of transition metals has been explored. This method is operationally simple, scalable, and applicable to late-stage azidation of natural products and derivatives, which make it a valuable method for the synthesis of organic azides.

One-Pot Aminoethylation of Indoles/Pyrroles with Alkynes and Sulfonyl Azides.

A general and efficient one-pot aminoethylation of substituted indoles/pyrroles was accomplished for the synthesis of various tryptamine derivatives employing a combination of alkynes and sulfonyl azides as readily accessible aminoethylating agents. The reaction features a successful integration of copper-catalyzed alkyne and azide cycloaddition to N-sulfonyl-1,2,3-triazole, rhodium-catalyzed selective insertion of α-iminocarbenes onto the C3-H bond of indoles, and reduction of the resultant enamides to tryptamine derivatives employing either NaCNBH3 or palladium catalyst, in one-pot. The reaction also showed excellent functional-group tolerance and allowed the synthesis of various substituted tryptamines in good to excellent yield. This transformation constitutes a one-pot formal regioselective functionalization of terminal alkynes. Utility of the synthesized tryptamine was further demonstrated in the synthesis of dihydro-β-carboline and tryptoline.

Copper(I)-Y Zeolite-Catalyzed Regio- and Stereoselective [2 + 2 + 2] Cyclotrimerization Cascade: An Atom- and Step-Economical Synthesis of Pyrimido[1,6-a]quinoline.

An elegant copper(I)-Y zeolite-catalyzed tandem process, involving ketenimine-based termolecular [2 + 2 + 2]/[NC + CC + NC] cycloaddition, using sulfonyl azide, alkyne, and quinoline, to prepare pyrimido[1,6-a]quinolines is reported. In this straightforward, highly atom- and step-economical protocol, copper(I) promotes for azide-alkyne [3 + 2] cycloaddition which is followed by ring-rearrangement/ketenimine formation/regio- and stereoselective [2 + 2 + 2] termolecular cycloaddition and dehydrogenation cascade to yield selectively the E-isomer of pyrimido[1,6-a]quinoline.

ChemInform Abstract: Construction of Multifunctional 3‐Amino‐2‐carbamimidoylacrylamides and Their Crystalline Channel‐Type Inclusion Complexes.

AbstractA copper‐catalyzed three‐component coupling reaction of sulfonyl azides, propiolamides, and amidines affords the title compounds.

Reactions of Thioacetamide Derivatives with Sulfonyl Azides: An Approach to Active‐Methylene N‐Sulfonylacetamidines

AbstractReactions of functionalized [CN, CO2Et, C(O)NHR, C(S)NR1R2] derivatives of thiomalonic acid and 2‐arylthioacetamides with sulfonyl azides were shown to give active‐methylene N‐sulfonylamidines in 62–98 % yields. Various procedures for the reactions, including the use of pyridine, boiling ethanol, and water, or running the reactions in the absence of a base and solvent at 80 °C, were carried out and compared. The solvent‐free variant was the best in terms of yield, and also because it does not require the use of an excess of the toxic and hazardous azides. The reaction was shown to tolerate electron‐withdrawing substituents such as carbonyl, cyano, and aryl groups at the C‐2 position. The presence of alkyl and phenyl groups on the nitrogen atom of the thioacetamide fragment, and the presence of substituents on the sulfonyl group were also tolerated. Thus, an efficient solvent‐free, catalyst‐free, and base‐free synthetic approach for the synthesis of N‐sulfonylmalonacetamidines and 2‐arylacetamidines was found.

ChemInform Abstract: Nanoparticulate Copper(II) Oxide Catalyzed Synthesis of Guanidine Derivatives and Their Conversion into Functionalized Iminoguanidines.

AbstractA simple multicomponent approach for the synthesis of a novel class of iminoguanidine derivatives involving a nano‐copper(II) catalyzed tandem reaction of anilines, di(cyclo)alkylcarbodiimides, sulfonyl azides, and terminal alkynes is developed.

ChemInform Abstract: Facile Synthesis of 2,5‐Disubstituted Thiazoles from Terminal Alkynes, Sulfonyl Azides, and Thionoesters.

AbstractProcedures are evaluated for the preparation of various thiazole structures either from triazole precursors (prepared from terminal alkynes and sulfonyl azides) or directly starting with their formation in a one‐pot approach.

Rearrangement Reactions of Tritylcarbenes: Surprising Ring Expansion and Computational Investigation

As a rule, acetylides and sulfonyl azides do not undergo electrophilic azide transfer because 1,2,3-triazoles are usually formed. We show now that treatment of tritylethyne with butyllithium followed by exposure to 2,4,6-triisopropylbenzenesulfonyl azide leads to products that are easily explained through the generation of short-lived tritylethynyl azide and its secondary product cyanotritylcarbene. Furthermore, it is demonstrated that tritylcarbenes generally do not produce triphenylethenes exclusively, as was stated in the literature. Instead, these carbenes always yielded also (diphenylmethylidene)cycloheptatrienes (heptafulvenes) as side products. This result is supported by static DFT, coupled cluster, and ab initio molecular dynamics calculations. From these investigations, the fused bicyclobutane intermediate was found to be essential for heptafulvene formation. Although the bicyclobutane is also capable of rearranging to the triphenylethene product, only the heptafulvene pathway is reasonable from the energetics. The ethene is formed straight from cyanotritylcarbene.

Iridium-catalyzed direct ortho -C H amidation of benzoic acids with sulfonylazides

Abstract A mild and efficient iridium-catalyzed ortho-C H amidation with sulfonyl azides by weakly coordinating carboxylic acid was demonstrated, which provided a novel approach to anthranilic acid derivatives.

ChemInform Abstract: Copper‐Catalyzed Synthesis of Pentasubstituted Pyridines from N‐Sulfonyl Ketenimines, 1,1,3,3‐Tetramethylguanidine, and Acetylene Dicarboxylates.

Regioselective synthesis of pentasubstituted pyridines has been developed in moderate-to-good yields by the reaction of sulfonyl azides, alkynes, and a dialkyl acetylenedicarboxylatetetramethylguanidine adduct catalyzed by CuI in MeCN at room temperature.

ChemInform Abstract: Direct C—H Amidation of Benzoic Acids to Introduce meta‐ and para‐Amino Groups by Tandem Decarboxylation.

AbstractProcedure A) is found to be optimal for the introduction of an amino function in ortho‐position to the carboxylic acid by use of different sulfonyl azides.

Iridium-Catalyzed Direct C-H Sulfamidation of Aryl Nitrones with Sulfonyl Azides at Room Temperature.

Ir(III)-catalyzed direct C-H sulfamidation of aryl nitrones has been developed to synthesize various sulfamidated nitrones in moderate to excellent yields with excellent regioselectivity and broad functional group tolerance. This transformation could proceed smoothly at room temperature with low catalyst loading in the absence of external oxidants, acids, or bases. Molecular nitrogen was released as the sole byproduct, thus providing an environmentally benign sulfamidation process. And this protocol could efficiently apply to synthesize the substituted benzisoxazoline via one-step transformation from the product.

Cu(I)/Rh(II)-Catalyzed Tandem Convergent Multicomponent Reaction for the Regio- and Stereocontrolled Synthesis of γ-Oxo-β-amino Esters.

The first example of a highly regio- and stereoselective catalytic method for the three-component one-pot synthesis of highly functionalized α-vinylated γ-oxo-β-amino esters is disclosed. In this catalytic triad, the Cu(I)-catalyst selectively catalyzes the cycloaddition of the 1-alkyne and sulfonyl azide first resulting in the corresponding 1-sulfonyl-1,2,3-triazole. An α-imino Rh(II)-carbene is generated from an open-chain α-imino diazo of the triazole, and this species reacts with γ-hydroxy α,β-unsaturated esters to form allylic (Z)-amino vinyl ethers. Rapid deconjugative [3,3]-sigmatropic rearrangement affords the α-vinyl γ-oxo-β-amino esters in high yields with high levels of diastereoselectivity.

ChemInform Abstract: Iridium(III)‐Catalyzed Benzylic Amine Directed C—H Sulfonamidation of Arenes with Sulfonyl Azides.

ChemInformVolume 46, Issue 29 Preparative Organic Chemistry ChemInform Abstract: Iridium(III)-Catalyzed Benzylic Amine Directed C—H Sulfonamidation of Arenes with Sulfonyl Azides. Heng Chen, Heng Chen Discovery Chem. Group, Genentech Inc., South San Francisco, CA 94080, USASearch for more papers by this authorMalcolm P. Huestis, Malcolm P. Huestis Discovery Chem. Group, Genentech Inc., South San Francisco, CA 94080, USASearch for more papers by this author Heng Chen, Heng Chen Discovery Chem. Group, Genentech Inc., South San Francisco, CA 94080, USASearch for more papers by this authorMalcolm P. Huestis, Malcolm P. Huestis Discovery Chem. Group, Genentech Inc., South San Francisco, CA 94080, USASearch for more papers by this author First published: 02 July 2015 https://doi.org/10.1002/chin.201529052Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume46, Issue29July, 2015 RelatedInformation

Three-Component Functionalized Dihydropyridine Synthesis via a Formal Inverse Electron-Demand Hetero-Diels-Alder Reaction.

A mild three-component synthetic approach to versatile 2-amino-1,4-dihydropyridines from terminal alkynes, sulfonyl azides, and N-sulfonyl-1-aza-1,3-butadienes was successfully developed and relied on the in situ generation of metalated ynamide intermediates Ib to achieve a formal inverse electron-demand hetero-Diels-Alder reaction. Experimental results suggest that alkali metal cations (Li(+) and Cs(+) ions) might play a critical role to achieve the cycloaddition process.

ChemInform Abstract: Rhodium‐Catalyzed Regioselective Direct C—H Amidation of 2,4‐Diarylquinazoline with Sulfonyl Azides: An Example of Steric Hindrance Regulated Mono‐ and Diamidation Selectivity.

AbstractAn unprecedented steric hindrance controlled regioselective rhodium‐catalyzed direct C—H amidation of 2,4‐diarylquinazoline is described.

Microwave-Assisted Copper-Catalyzed Four-Component Tandem Synthesis of 3-N-Sulfonylamidine Coumarins.

Microwave-assisted copper-catalyzed four-component tandem synthesis of 3-N-sulfonylamidine coumarins has been accomplished by the coupling of salicylaldehydes, propiolates, sulfonyl azides, and secondary amines. This one-pot protocol affords an effective route for the construction of functionalized coumarin structural frameworks in a single operation with moderate to high yields.

Synthesis of 2-Alkoxyaryl-2-aryl Enamines via Tandem Copper-Catalyzed Cycloaddition and Rhodium-Catalyzed Alkoxyarylation from Alkynes, N-Sulfonyl Azides, and Aryl Ethers.

A synthetic route to a wide range of 2-alkoxyaryl-2-aryl enamines is developed from Rh-catalyzed alkoxyarylation of N-sulfonyl-4-aryl-1,2,3-triazoles with aryl ethers via the elimination of nitrogen molecule. In addition, 2-alkoxyaryl-2-aryl enamines are prepared via tandem Cu-catalyzed cycloaddition and Rh-catalyzed alkoxyarylation starting from alkynes, N-sulfonyl azides, and aryl ethers in one-pot.