Synthesis of Enantioenriched Pyrrolidines via Gold-Catalyzed Tandem Cycloisomerization/Hydrogenation of Chiral Homopropargyl Sulfonamides

Yu, Yanlin; Shu, Chao; Tan, Tong‐De; Li, Long; Rafique, Shahid; Ye, Long‐Wu

doi:10.1021/acs.orglett.6b02736

Cited by 32 publications

(14 citation statements)

References 75 publications

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“…20 At the same time, Yu et al applied the gold-catalyzed tandem reductive cycloisomerization of cyclic homopropargyl sulfonamides for the synthesis of N -tosyl-protected compound 1c (method D). 14 In 2017, Skvorcova and co-workers studied a rearrangement of N -protected spirocyclic (cyclopropylmethyl)amines promoted with trifluoroacetic acid (method E). 17 A related approach was described by Shi et al; it relied on the Au(I)-catalyzed reaction of methylenecyclopropanes with sulfonamides via a domino ring-opening–ring-closing–hydroamination sequence (method F).…”

Section: Introductionmentioning

confidence: 99%

Scalable Synthesis of Biologically Relevant Spirocyclic Pyrrolidines

et al. 2019

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Synthetic approaches toward multigram preparation of spirocyclic α,α-disubstituted pyrrolidines from readily available starting materials are discussed. It was shown that although a number of synthetic methodologies have been known to date, many of the title compounds remain hardly accessible. The most appropriate literature method (which relied on reaction of imines and allyl magnesium halide, followed by bromocyclization) was identified and optimized. It was found that the method is most fruitful for simple non-functionalized substrates. Two novel approaches based on the Sakurai or Petasis reactions of cyclic ketones, followed by hydroboration–oxidation at the allyl moiety thus introduced, were elaborated. The latter method had the largest scope and was beneficial for the substrates containing organosulfur or protected amino functions. For the synthesis of 4-azaspiro[2.4]heptane, an alternative synthetic scheme commencing from tert -butyl cyclopropanecarboxylate (instead of the corresponding ketone) was developed. It was shown that the whole set of the methodologies developed can be used for the synthesis of various spirocyclic α,α-disubstituted pyrrolidines—advanced building blocks of potential importance to medicinal and agrochemistry—at up to a 100 g scale.

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Section: Introductionmentioning

confidence: 99%

Scalable Synthesis of Biologically Relevant Spirocyclic Pyrrolidines

et al. 2019

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“…[5c] While silver-catalyzed 5-endo-dig cyclization of N-Ts propargylamine leading to dihydropyrrole has been reported, [24] cyclization of N-arylated counterparts needed, in general, as toichiometric amount of silver salt to afford directly N-arylated pyrrole because of the in situ oxidation of the dihydropyrrole to pyrrole. [25][26][27] However,this step was not happening in our case.W ea ssumed that the presence of isocyanide in the reaction mixture effectively bypassed this undesired side reaction, thus leading efficiently to N-arylated dihydropyrrole.…”

Section: Zuschriftenmentioning

confidence: 59%

Silver‐Catalyzed Three‐Component 1,1‐Aminoacylation of Homopropargylamines: α‐Additions for Both Terminal Alkynes and Isocyanides

et al. 2017

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The reaction of secondary homopropargylamines, isocyanides,and water in the presence of acatalytic amount of silver acetate and subsequent purification by chromatography on silica gel afforded substituted proline amides in good to excellent yields.P rimary homopropargylamines underwent ac yclizative Ugi-JoulliØ three-component reaction with isocyanides and carboxylic acids to affordf unctionalizedN -acyl proline amides.H igh diastereoselectivity was observed in the synthesis of 4-alkoxy and 4,5-disubstituted proline derivatives. This work represents the first examples of at hree-component cyclizative 1,1-aminoacylation of terminal alkynes.

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“…At the outset of the reaction, the Au(I)‐catalyzed regioselective cycloisomerization of amine bridged enynes 311 via 5‐ exo ‐dig mode 311 a results in an N‐allylic enamine intermediate 312 , which sequentially participates in the Pd(0)/Brønsted acid catalyzed allylic alkylation ( 312 a ) to form dihydropyrrole derivatives 313 [388] . Pyrrolidines can also be retrieved selectively through a tandem 5‐ exo ‐ dig Markovnikov cycloisomerization/hydrogenation of 4‐pentyn‐1‐amides employing Et 3 PAuNTf 2 (5.0 mol %) and i Pr 3 SiH (3.0 equiv) as catalyst and hydrogenation source respectively [389] . Arcadi's team unveiled the Au(I)‐catalyzed cyclization/condensation cascade of symmetrical and unsymmetrical 2‐[(2‐aminophenyl)ethynyl]phenylamines with aldehydes to achieve the synthesis of indolo[3,2‐ c ]quinolone derivatives.…”

Section: Cyclization Of Nitrogen‐centred Nucleophiles Towards C−c Multiple Bondsmentioning

confidence: 99%

Cycloisomerization of π‐Coupled Heteroatom Nucleophiles by Gold Catalysis: En Route to Regiochemically Defined Heterocycles

Praveen

2021

The Chemical Record

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Since the dawn of millennium, catalytic gold chemistry is at the forefront to set off diverse organic reactions via unique activation of π‐bonded molecules. Within this purview, cycloisomerization of heteroatom nucleophiles linked to a π‐system is one of the well recognized chemistry for the construction of numerous heterocyclic cores. Though the rudimentary aspects of this transformation are reviewed by several groups in different timeline, a holistic view on regiochemistry of such reactions went largely overlooked. Hence, this account emphasizes the gold catalyzed regioselective cycloisomerization of structurally distinctive π‐connected hetero‐nucleophiles leading to different heterocycles documented in the last two decades. From an application perspective, this account also highlights those methodologies which find a role in the total synthesis of natural products. Wherever appropriate, mechanistic details and contributing factors for selectivity are also discussed.

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Synthesis of Enantioenriched Pyrrolidines via Gold-Catalyzed Tandem Cycloisomerization/Hydrogenation of Chiral Homopropargyl Sulfonamides

Cited by 32 publications

References 75 publications

Scalable Synthesis of Biologically Relevant Spirocyclic Pyrrolidines

Scalable Synthesis of Biologically Relevant Spirocyclic Pyrrolidines

Silver‐Catalyzed Three‐Component 1,1‐Aminoacylation of Homopropargylamines: α‐Additions for Both Terminal Alkynes and Isocyanides

Cycloisomerization of π‐Coupled Heteroatom Nucleophiles by Gold Catalysis: En Route to Regiochemically Defined Heterocycles

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