Synthesis and Reaction of 1-Azabicyclo[3.1.0]hexane

Hayashi, Kazuhiko; Kujime, Eiko; Katayama, Hajime; Sano, Shigeki; Shiro, Motoo; Nagao, Yoshimitsu

doi:10.1248/cpb.57.1142

Cited by 8 publications

(4 citation statements)

References 22 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Since tertiary bicyclic aziridines are found in natural products such as azinomycin A and ficellomycin, the formation of these ring systems is critical for synthetic medicinal chemistry . Surprisingly few reactions of this type have been demonstrated, and the most common synthetic approach for forming this class of bicyclic aziridines is through a ring closing of a cyclic halo-amine, such as 2-(bromomethyl)pyrrolidine …”

Section: Results and Discussionmentioning

confidence: 99%

Synthesis of Fully Aliphatic Aziridines with a Macrocyclic Tetracarbene Iron Catalyst

2016

View full text Add to dashboard Cite

A second-generation aziridination catalyst supported by a borate-based dianionic macrocyclic tetracarbene ligand has been synthesized. The new macrocyclic tetracarbene iron(II) complex catalyzed the aziridination of alkyl azides and aliphatic alkenes showcasing the first fully aliphatic version of this C 2 + N 1 reaction. High isolated yields were obtained when no functional groups were present on the organic azides and alkenes, while modest yields were achieved when nonprotic functional groups were included. Even multiple functional groups can be added to the azide and alkene fragments to produce the most complex aziridines yet synthesized by this C 2 + N 1 catalytic reaction. The catalyst generated higher yields for aziridination with aryl azides and alkenes than the previously reported catalyst, [( Me,Et TC Ph )Fe(NCCH 3 ) 2 ](PF 6 ) 2 . The contrast is particularly apparent with functionalized aryl azides where the second-generation catalyst now provides practical yields for synthetic chemistry. Finally, catalytic intramolecular aziridination was investigated since many natural products with aziridines feature bicyclic tertiary aziridines. For fiveand six-membered rings, the bicyclic aziridines were formed catalytically, in contrast to previously studied catalyzed and uncatalyzed reactions.

show abstract

Section: Results and Discussionmentioning

confidence: 99%

Synthesis of Fully Aliphatic Aziridines with a Macrocyclic Tetracarbene Iron Catalyst

2016

View full text Add to dashboard Cite

show abstract

“…1‐Azabicyclo[3.1.0]hexane 101 has also been employed as a starting material in the synthesis of a variety of 2‐(chloromethyl)pyrrolidines 103 / 105 and 3‐halopiperidines 104 / 106 (Scheme ) . Reaction of azabicycle 101 with acyl halides resulted mainly in the formation of the corresponding pyrrolidines 103 , whereas treatment of the same starting material with a range of alkyl halides afforded piperidines 106 as the major compounds, apart from the reaction with bromoacetonitrile (R 2 =CN) yielding the corresponding pyrrolidine 105 as the main constituent.…”

Section: Preparation and Synthetic Utilization Of Bicyclic Aziridinimentioning

confidence: 99%

Bicyclic Aziridinium Ions in Azaheterocyclic Chemistry – Preparation and Synthetic Application of 1‐Azoniabicyclo[n.1.0]alkanes

et al. 2016

View full text Add to dashboard Cite

Scheme 4. Possible isomerizations of bicyclic aziridiniumi ntermediates 10. Scheme5.Reactiono f1 -azabicyclo[1.1.0]butane 16 with aromatic thiols and amines. Scheme 10. Solvent-dependent transformation of 2-(bromomethyl)aziridines 35. Scheme 9. Reduction of amines 33 and 39 to aziridines 34 and azetidines 38. Scheme 14. Nucleophile-dependent conversion of mesyloxyazetidine 52. Scheme 15. Ring contraction of 3,3-dichloroazetidines 55 to aziridines 60. Scheme 19. Ring expansion of 2-chloromethyl-a nd 2-(methanesulfonyloxymethyl)azetidines 72 to 3-substituted pyrrolidines 73 and 74. Scheme 20. DAST-promoted ring expansion of 2-(hydroxymethyl)azetidines 76. Scheme 40. Conversion of 1-azabicyclo[4.1.0]heptanes 159 to (thio)morpholines 161 and (thi)azepanes 163.

show abstract

“…7 The analytical data of all known aziridines are identical to those data previously reported in the literature. [17][18][19][20][21][22][23][24][25] Aliphatic Amino Alcohol Hydrogen Sulfates 2; General Procedure A 150-mL, two-necked, round-bottom flask was fitted with a magnetic stirrer bar and an addition funnel. The flask was charged with a vicinal amino alcohol (10 mmol) and Et 2 O (100 mL).…”

Section: Scheme 3 Synthesis Of Aziridines From Amino Alcoholsmentioning

confidence: 99%

An Improved and Mild Wenker Synthesis of Aziridines

Li¹,

Chen²,

Xu³

2010

Synthesis

View full text Add to dashboard Cite

The conventional Wenker synthesis of aziridines from vicinal amino alcohols has been modified by employing mild reaction conditions. Amino alcohols were converted into their hydrogen sulfates with chlorosulfonic acid. The sulfates were cyclized with sodium hydroxide, and even with non-nucleophilic sodium carbonate. The current, improved method extends the scope of the typical Wenker synthesis and is applicable to unstable amino alcohols in hot sulfuric acid and to unstable sulfates which favor elimination and hydroxide displacement in the presence of strong base.

show abstract

Synthesis and Reaction of 1-Azabicyclo[3.1.0]hexane

Cited by 8 publications

References 22 publications

Synthesis of Fully Aliphatic Aziridines with a Macrocyclic Tetracarbene Iron Catalyst

Synthesis of Fully Aliphatic Aziridines with a Macrocyclic Tetracarbene Iron Catalyst

Bicyclic Aziridinium Ions in Azaheterocyclic Chemistry – Preparation and Synthetic Application of 1‐Azoniabicyclo[n.1.0]alkanes

An Improved and Mild Wenker Synthesis of Aziridines

Contact Info

Product

Resources

About