Sulfamate-derived Cyclic Imines Research Articles

Asymmetric Construction of Chiral 2-Azetines and Axially Chiral Tetrasubstituted Allenes via Phosphine Catalysis.

Chiral 2-azetines and allenes are highly valuable structural units in natural products and useful chemicals. However, enantioselective synthesis of both 2-azetines and allenes has been extremely challenging. Herein, we present asymmetric construction of chiral 2-azetines (70-98% yields and up to 96% ee) through chiral phosphine-catalyzed [2+2] annulation of yne-enones with sulfamate-derived cyclic imines. These 2-azetines were easily transformed into chiral allenes upon treatment with Et3SiH, BF3•Et2O and water at rt for 2 minutes. Based on the above transformations, a concise one-pot synthetic procedure combining [2+2] annulation of yne-enones and sulfamate-derived cyclic imines under phosphine catalysis and sequential reduction/isomerization/ring-opening reaction through Et3SiH, BF3•Et2O and water was thus set up, providing axially chiral tetrasubstituted allenes in satisfactory yields and enantioselectivities (56-90% yields and up to 91% ee).

Annulation Reactions of Isoquinolinium Ylides with Sulfamate-Derived Cyclic Imines toward Polycyclic 1,3-Benzoxazepine Heterocycles

AbstractA dearomatization-guided and (3+2) cycloaddition-triggered annulation reaction of in situ formed isoquinolinium ylides with sulfamate-derived cyclic imines is reported, offering a cogent synthesis of tetracyclic 1,3-benzoxazepine frameworks in high yields. The protocol features successive ring-forming and ring-breaking events in a cascade fashion and is also scalable.

Palladium-catalyzed [3 + 2] cycloaddition of 4-vinyl-4-butyrolactones with sulfamate-derived cyclic imines: construction of sulfamate-fused pyrrolidines.

The palladium-catalyzed [3 + 2] decarboxylative cycloaddition of 4-vinyl-4-butyrolactones with sulfamate-derived cyclic imines has been developed, providing the sulfamate-fused pyrrolidine derivatives in high yields with good diastereoselectivities. The scale-up reaction and further derivation of the product worked well, demonstrating the potential application of the current reaction in organic synthesis. A plausible reaction mechanism was also proposed.

Palladium-catalyzed [4 + 2] cycloaddition of 2-methylidenetrimethylene carbonate or methylene cyclic carbamate with sulfamate-derived cyclic imines.

A palladium-catalyzed [4 + 2] cycloaddition of 2-methylidenetrimethylene carbonate or methylene cyclic carbamate with sulfamate-derived cyclic imines has been successfully developed under mild reaction conditions, affording pharmacologically interesting oxazine or hydropyrimidine derivatives in high yields (up to 99% yield). Furthermore, the cycloaddition reactions could be efficiently scaled up and several synthetic transformations were accomplished for the construction of other useful 1,3-oxazine and hydropyrimidinone derivatives.

Ligand-Controlled Regiodivergent Asymmetric [5 + 2] and [3 + 2] Annulations of Vinyl Indoloxazolidones Catalyzed by Palladium.

Here, we present palladium-catalyzed regiodivergent asymmetric annulations of vinyl indoloxazolidones, which can act as 1,5-carbodipoles or 1,3-carbodipoles by tuning the chiral ligands and conditions, in the assemblies with sulfamate-derived cyclic imines and even activated alkenes. A diversity of polycyclic products are generally constructed with high regio- and enantioselectivity.

Annulation Cascade of Sulfamate-Derived Cyclic Imines with Glycine Aldimino Esters: Synthesis of 1,3-Benzoxazepine Scaffolds.

An efficient (3 + 2) cycloaddition triggered annulation is reported to access 1,3-benzoxazepine frameworks. With amine base, sulfamate-derived cyclic imines readily react with glycine aldimino esters to furnish benzo-fused seven-membered heterocyclic products in good yields. The cascade reaction involves the formation of one C-C, one C-N, and one C-O bond along with the cleavage of two C-N bonds and one S-O bond. The synthesis of o-tyrosine analogues has also been accomplished from annulation products.

Synthesis of Sulfamate-Fused 2-Aminopyrroles via an Isocyanide-Based Three Component [1+2+2] Annulation.

An efficient preparation of sulfamate-fused 2-aminopyrroles was achieved through an isocyanide-based three-component [1+2+2] annulation of isocyanides, dialkyl acetylenedicarboxylates, and sulfamate-derived cyclic imines in good to excellent yields (up to 99 %). This reaction proceeds smoothly without any activation or modification of substances under neutral and metal-free conditions. The reaction could also be conveniently performed on a gram scale.

Regio- and Diastereoselective Access to 4-Imidazolidinones via an Aza-Mannich Initiated Cyclization of Sulfamate-Derived Cyclic Imines with α-Halo Hydroxamates.

An efficient regio- and diastereoselective cyclization of sulfamate-derived cyclic imines with unsubstituted or monosubstituted α-halo hydroxamates is developed under mild conditions. This reaction proceeds smoothly under transition-metal-free conditions via a domino aza-Mannich addition/intramolecular nucleophilic substitution sequence, providing a convenient route to access 2-monosubstituted and 2,5-disubstituted 4-imidazolidinones. Notably, the products were obtained with single trans-isomers in moderate to excellent yields.

Phosphine-Catalyzed [3+2] Annulation of β-Sulfonamido-Substituted Enones with Sulfamate-Derived Cyclic Imines.

Phosphine-catalyzed [3+2] annulation of β-sulfonamido-substituted enones and sulfamate-derived cyclic imines has been developed, giving a series of imidazoline derivatives in moderate to excellent yields with good to excellent diastereoselectivities. A scale-up reaction worked well under mild reaction conditions. A possible mechanism was proposed on the basis of the results obtained.

Enantioselective Construction of Tetrahydroquinazoline Motifs via Palladium-Catalyzed [4 + 2] Cycloaddition of Vinyl Benzoxazinones with Sulfamate-Derived Cyclic Imines.

A palladium-catalyzed enantioselective [4 + 2] cycloaddition reaction of vinyl benzoxazinones with sulfamate-derived cyclic imines is described, affording the tetrahydroquinazolines bearing several functional rings in high yields (up to 99% yield) with good to excellent diastereoselectivities and excellent enantioselectivities (up to 96% ee). This reaction represents the first Pd-catalyzed asymmetric decarboxylative cycloaddition of vinyl benzoxazinones with imines.

Pd-Catalyzed diastereoselective [3 + 2] cycloaddition of vinylcyclopropanes with sulfamate-derived cyclic imines.

The palladium-catalyzed diastereoselective [3 + 2] cycloaddition reaction of vinylcyclopropanes with sulfamate-derived cyclic imines worked efficiently under mild reaction conditions, providing 2,3-dihydrobenzo[e]pyrrolo[1,2-c][1,2,3]oxathiazine 5,5-dioxide derivatives in good to excellent yields.

Phosphine-Catalyzed [4 + 2] Annulation of Allenoate with Sulfamate-Derived Cyclic Imines: A Reaction Mode Involving γ'-Carbon of α-Substituted Allenoate.

A phosphine-catalyzed [4 + 2] cycloaddition of cyclic α-substituted allenoates with sulfamate-derived cyclic imines has been reported. Using dibenzylphenylphosphine as the nucleophilic catalyst, the reaction worked efficiently to yield various fused multicyclic heterocyclic compounds in high yields with excellent diastereoselectivities. It undergoes a new reaction mode involving γ'-carbon of α-substituted allenoate.

Palladium-Catalyzed [5 + 2] Cycloaddition of Vinyloxiranes with Sulfamate-Derived Cyclic Imines To Construct 1,3-Oxazepine Heterocycles.

Palladium-catalyzed [5 + 2] cycloaddition of 2-aryl-2-vinyloxiranes with sulfamate-derived cyclic imines is described. The zwitterionic allylpalladium intermediates act as five-membered synthon to react with sulfamate-derived cyclic imines to furnish [5 + 2] cycloaddition, giving 1,3-oxazepine derivatives in moderate to excellent yields with excellent regioselectivities.

ChemInform Abstract: DABCO‐Catalyzed [3 + 2] Annulation of Sulfamate‐Derived Cyclic Imines with Isocyanoacetates: Synthesis of Sulfamate‐Fused 2‐Imidazoline.

DABCO-catalyzed [3 + 2] annulation reaction of sulfamate-derived cyclic imines with isocyanoacetate proceeds under mild conditions, providing sulfamate-fused 2-imidazolines in moderate to excellent yields with moderate to excellent diastereoselectivities.

DABCO-catalyzed [3 + 2] annulation of sulfamate-derived cyclic imines with isocyanoacetates: synthesis of sulfamate-fused 2-imidazoline.

DABCO-catalyzed [3 + 2] annulation reaction of sulfamate-derived cyclic imines with isocyanoacetate proceeds under mild conditions, providing sulfamate-fused 2-imidazolines in moderate to excellent yields with moderate to excellent diastereoselectivities.

ChemInform Abstract: PPh3‐Catalyzed Ring‐Expansion Reactions of Sulfamate‐Derived Cyclic Imines with Acetylenedicarboxylates.

The PPh3-catalyzed ring-expansion reaction of sulfamate-derived cyclic imines with acetylenedicarboxylates has been developed. The reaction works quite efficiently under very mild conditions to afford benzo[g][1,2,3]oxathiazocine-4,5-dicarboxylate 2,2-dioxide derivatives in high yields.

ChemInform Abstract: Phosphine‐Catalyzed [3 + 2] Cycloaddition of Sulfamate‐Derived Cyclic Imines with Allenoate: Synthesis of Sulfamate‐Fused Dihydropyrroles.

ChemInformVolume 45, Issue 5 Heterocyclic Compounds ChemInform Abstract: Phosphine-Catalyzed [3 + 2] Cycloaddition of Sulfamate-Derived Cyclic Imines with Allenoate: Synthesis of Sulfamate-Fused Dihydropyrroles. Hao Yu, Hao Yu Dep. Appl. Chem., Chin. Agric. Univ., Beijing 100193, Peop. Rep. ChinaSearch for more papers by this authorLei Zhang, Lei Zhang Dep. Appl. Chem., Chin. Agric. Univ., Beijing 100193, Peop. Rep. ChinaSearch for more papers by this authorZhilin Yang, Zhilin Yang Dep. Appl. Chem., Chin. Agric. Univ., Beijing 100193, Peop. Rep. ChinaSearch for more papers by this authorZhen Li, Zhen Li Dep. Appl. Chem., Chin. Agric. Univ., Beijing 100193, Peop. Rep. ChinaSearch for more papers by this authorYan Zhao, Yan Zhao Dep. Appl. Chem., Chin. Agric. Univ., Beijing 100193, Peop. Rep. ChinaSearch for more papers by this authorYumei Xiao, Yumei Xiao Dep. Appl. Chem., Chin. Agric. Univ., Beijing 100193, Peop. Rep. ChinaSearch for more papers by this authorHongchao Guo, Hongchao Guo Dep. Appl. Chem., Chin. Agric. Univ., Beijing 100193, Peop. Rep. ChinaSearch for more papers by this author Hao Yu, Hao Yu Dep. Appl. Chem., Chin. Agric. Univ., Beijing 100193, Peop. Rep. ChinaSearch for more papers by this authorLei Zhang, Lei Zhang Dep. Appl. Chem., Chin. Agric. Univ., Beijing 100193, Peop. Rep. ChinaSearch for more papers by this authorZhilin Yang, Zhilin Yang Dep. Appl. Chem., Chin. Agric. Univ., Beijing 100193, Peop. Rep. ChinaSearch for more papers by this authorZhen Li, Zhen Li Dep. Appl. Chem., Chin. Agric. Univ., Beijing 100193, Peop. Rep. ChinaSearch for more papers by this authorYan Zhao, Yan Zhao Dep. Appl. Chem., Chin. Agric. Univ., Beijing 100193, Peop. Rep. ChinaSearch for more papers by this authorYumei Xiao, Yumei Xiao Dep. Appl. Chem., Chin. Agric. Univ., Beijing 100193, Peop. Rep. ChinaSearch for more papers by this authorHongchao Guo, Hongchao Guo Dep. Appl. Chem., Chin. Agric. Univ., Beijing 100193, Peop. Rep. ChinaSearch for more papers by this author First published: 16 January 2014 https://doi.org/10.1002/chin.201405118Read 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. Volume45, Issue5February 4, 2014 RelatedInformation

Phosphine-catalyzed [4+2] cycloaddition of sulfamate-derived cyclic imines with allenoates: synthesis of sulfamate-fused tetrahydropyridines

Using n-PrPPh2 as the nucleophilic catalyst, the [4+2] cycloaddition reaction of the sulfamate-derived cyclic imines with allenoates works efficiently to yield various sulfamate-fused tetrahydropyridines in high yields with excellent diastereoselectivities. Using amino acid-based bifunctional phosphine as chiral catalyst, an asymmetric [4+2] cycloaddition reaction was achieved, giving chiral sulfamate-fused tetrahydropyridines in high yields with good enantiomeric excesses.

PPh3‐Catalyzed Ring‐Expansion Reactions of Sulfamate‐Derived Cyclic Imines with Acetylenedicarboxylates

The PPh3-catalyzed ring-expansion reaction of sulfamate-derived cyclic imines with acetylenedicarboxylates has been developed. The reaction works quite efficiently under very mild conditions to afford benzo[g][1,2,3]oxathiazocine-4,5-dicarboxylate 2,2-dioxide derivatives in high yields.

Phosphine-Catalyzed [3 + 2] Cycloaddition of Sulfamate-Derived Cyclic Imines with Allenoate: Synthesis of Sulfamate-Fused Dihydropyrroles

Ph3P-catalyzed [3 + 2] cycloaddition reaction of sulfamate-derived cyclic imines with allenoate has been developed, affording sulfamate-fused dihydropyrroles under very mild conditions in high yields. Using amino acid-based bifunctional phosphine as chiral catalyst, its asymmetric variant provided the corresponding products in good yields with moderate to excellent enantiomeric excesses (up to 91% yield and up to 98% ee). Subsequent transformations of the heterocyclic products gave various pharmaceutically attractive compounds.