174714-18-2

Upstream product

• 1066-54-2 trimethylsilylacetylene 
• 174714-14-8 (S)-2-(Trimethylsilanylmethyl-amino)-propan-1-ol 
• 154557-47-8 (S)-2-(Benzyl-trimethylsilanylmethyl-amino)-propan-1-ol 
• 174714-19-3 (3R,4S)-4-(Benzyl-trimethylsilanylmethyl-amino)-1-trimethylsilanyl-pent-1-yn-3-ol 
• 154557-48-9 (S)-2-(Benzyl-trimethylsilanylmethyl-amino)-propionaldehyde 
• 108-24-7 acetic anhydride 
• 174714-17-1 (Z)-(3R,4S)-4-(Benzyl-trimethylsilanylmethyl-amino)-1-trimethylsilanyl-pent-1-en-3-ol 

Downstream Products

• 174714-10-4 (2S,3R)-1-benzyl-2-methyl-1,2,3,6-tetrahydropyridin-3-ol 
• 174714-13-7 Acetic acid (2S,3R)-1-benzyl-2-methyl-1,2,3,6-tetrahydro-pyridin-3-yl ester 

Relevant academic research and scientific papers

An Oxidative Mannich Cyclization Methodology for the Stereocontrolled Synthesis of Highly Functionalized Piperidines

Studies focusing on the development and application of a new oxidative methodology for promoting Mannich cyclizations have been conducted. The general features of these processes were explored with selected α-silylamino and α-silylamido allyl- and vinylsilanes. Representative conditions for affecting conversion of the α-silylamine and -amide functionalities into intermediate N-alkyl and N-acyliminium cations involve either 9,10-dicyanoanthracene SET-sensitized photooxidation or ceric ammonium or tetra-n-butylammonium nitrate oxidations. The applicability of these procedures for promoting Mannich cyclizations was first demonstrated by the preparation of methylidenepi- peridines and -hydroazepines. Further studies have led to observations which show that Mannich cyclizations of stereochemically labeled α-silylamino vinylsilanes proceed to furnish tetrahydro- pyridines. Also, unlike their amine analogues, α-silylamido (E)-vinylsilanes undergo cyclization to produce tetrahydropyridines with retention of absolute and relative stereochemistry. The differences are due to the fact that N-acyliminium cations serve as intermediates in reactions of the α-silylamide systems. Moreover, the oxidation procedure is ideally suited for intermediate N-acyliminium cation generation in stereocontrolled reactions of α-silylamido allylsilanes. Finally, the preparative utility of the new cyclization method, when used in conjunction with an α-amino acid based strategy for substrate generation, was demonstrated by applications in concise routes for the synthesis of the aza-sugars, (-)-1-deoxymannojirimycin and (+)-l-deoxyallonojirimycin.

Stereochemical features of oxidative Mannich cyclizations of vinyl- and allyl-silane containing α-silyl-amines and -amides

Studies of the new oxidative Mannich cyclization reaction of α-silyl-amines and -amides demonstrate advantageous features of the process when applied to stereocontrolled hydropyridine syntheses.