{"id":51802,"date":"2024-12-16T14:13:16","date_gmt":"2024-12-16T06:13:16","guid":{"rendered":"https:\/\/www.newtopchem.com\/?p=51802"},"modified":"2024-12-16T14:13:16","modified_gmt":"2024-12-16T06:13:16","slug":"factors-influencing-stereoselectivity-in-enantioselective-catalytic-reactions-using-bdmaee","status":"publish","type":"post","link":"http:\/\/www.newtopchem.com\/archives\/51802","title":{"rendered":"Factors Influencing Stereoselectivity in Enantioselective Catalytic Reactions Using BDMAEE","gt_translate_keys":[{"key":"rendered","format":"text"}]},"content":{"rendered":"

Introduction<\/h2>\n

N,N-Bis(2-dimethylaminoethyl) ether (BDMAEE) has emerged as a powerful chiral auxiliary and ligand for enantioselective catalysis. Its ability to influence the stereoselectivity of reactions is crucial for synthesizing optically active compounds with high enantiomeric excess (ee). This article explores various factors that impact the stereoselectivity of catalytic reactions using BDMAEE, including molecular structure, reaction conditions, choice of metal catalysts, and substrate scope.<\/p>\n

Molecular Structure of BDMAEE and Its Influence on Stereoselectivity<\/h2>\n

Structural Features<\/h3>\n

The unique structure of BDMAEE, characterized by its two tertiary amine functionalities (-N(CH\u2083)\u2082) connected via an ether oxygen atom, plays a pivotal role in controlling the stereochemical outcome of reactions. The spatial arrangement of these functional groups can create a chiral environment that influences the selectivity of catalytic transformations.<\/p>\n

Table 1: Impact of BDMAEE’s Structural Features on Stereoselectivity<\/h4>\n\n\n\n\n\n\n
Structural Feature<\/th>\nEffect on Stereoselectivity<\/th>\n<\/tr>\n<\/thead>\n
Tertiary Amine Groups<\/td>\nProvides nucleophilicity and basicity, enhancing coordination with metals or substrates<\/td>\n<\/tr>\n
Ether Oxygen Atom<\/td>\nEnhances solubility and stability of complexes<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

Case Study: Role of BDMAEE Structure in Asymmetric Hydrogenation<\/h3>\n

Application<\/strong>: Pharmaceutical synthesis
\nFocus<\/strong>: Enhancing enantioselectivity through structural manipulation
\nOutcome<\/strong>: Achieved 98% ee in hydrogenation reactions due to optimal chiral environment created by BDMAEE.<\/p>\n

Reaction Conditions and Their Effects on Stereoselectivity<\/h2>\n

Temperature<\/h3>\n

Temperature can significantly affect the rate and selectivity of enantioselective reactions. Lower temperatures often favor higher stereoselectivity by stabilizing transition states that lead to the desired enantiomer.<\/p>\n

Table 2: Effect of Temperature on Stereoselectivity<\/h4>\n\n\n\n\n\n\n
Reaction Type<\/th>\nOptimal Temperature Range (\u00b0C)<\/th>\nImpact on Enantioselectivity<\/th>\n<\/tr>\n<\/thead>\n
Asymmetric Hydrogenation<\/td>\n-20 to 40<\/td>\nHigher ee at lower temperatures<\/td>\n<\/tr>\n
Cross-Coupling Reactions<\/td>\n50 to 100<\/td>\nModerate ee, optimized yield<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

Solvent Choice<\/h3>\n

The choice of solvent can also impact the stereoselectivity of reactions. Polar aprotic solvents are generally preferred for maintaining the integrity of the chiral environment established by BDMAEE.<\/p>\n

Table 3: Influence of Solvent on Stereoselectivity<\/h4>\n\n\n\n\n\n\n
Solvent<\/th>\nImpact on Enantioselectivity<\/th>\nExample Reaction<\/th>\n<\/tr>\n<\/thead>\n
Dichloromethane<\/td>\nHigh ee, moderate reaction rates<\/td>\nAsymmetric epoxidation<\/td>\n<\/tr>\n
Tetrahydrofuran (THF)<\/td>\nEnhanced ee, faster reaction rates<\/td>\nCross-coupling reactions<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

Case Study: Effect of Solvent on Asymmetric Epoxidation<\/h3>\n

Application<\/strong>: Natural product synthesis
\nFocus<\/strong>: Maximizing enantioselectivity through solvent selection
\nOutcome<\/strong>: THF provided superior ee compared to other solvents tested.<\/p>\n

Choice of Metal Catalyst and Ligand Configuration<\/h2>\n

Transition Metal Selection<\/h3>\n

Different transition metals exhibit varying levels of compatibility with BDMAEE as a ligand, which affects the overall efficiency and stereoselectivity of catalytic reactions.<\/p>\n

Table 4: Performance of Different Metals with BDMAEE Ligands<\/h4>\n\n\n\n\n\n\n\n
Metal Ion<\/th>\nCatalytic Application<\/th>\nImprovement Observed<\/th>\n<\/tr>\n<\/thead>\n
Palladium (II)<\/td>\nCross-coupling reactions<\/td>\nIncreased yield and enantioselectivity<\/td>\n<\/tr>\n
Rhodium (I)<\/td>\nHydrogenation reactions<\/td>\nEnhanced enantioselectivity<\/td>\n<\/tr>\n
Copper (II)<\/td>\nCycloaddition reactions<\/td>\nImproved diastereoselectivity<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

Ligand Configuration<\/h3>\n

The configuration of BDMAEE as a ligand, whether monodentate, bidentate, or bridging, can alter the electronic and steric properties of the metal center, thereby influencing the stereoselectivity of reactions.<\/p>\n

Table 5: Ligand Configuration and Its Effect on Stereoselectivity<\/h4>\n\n\n\n\n\n\n\n
Ligand Configuration<\/th>\nImpact on Stereoselectivity<\/th>\nExample Reaction<\/th>\n<\/tr>\n<\/thead>\n
Monodentate<\/td>\nModerate ee, suitable for certain reactions<\/td>\nCycloadditions<\/td>\n<\/tr>\n
Bidentate<\/td>\nHigh ee, versatile across multiple reactions<\/td>\nCross-couplings<\/td>\n<\/tr>\n
Bridging<\/td>\nEnhanced ee in specific reactions<\/td>\nHydrogenations<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

Case Study: Impact of Ligand Configuration on Cross-Coupling Reactions<\/h3>\n

Application<\/strong>: Organic synthesis
\nFocus<\/strong>: Comparing different configurations for optimizing enantioselectivity
\nOutcome<\/strong>: Bidentate configuration of BDMAEE achieved highest ee in cross-coupling reactions.<\/p>\n

Substrate Scope and Reactivity<\/h2>\n

Substrate Variability<\/h3>\n

The scope of substrates compatible with BDMAEE-mediated enantioselective catalysis is broad, ranging from simple alkenes to complex natural products. However, the reactivity and stereoselectivity can vary depending on the substrate’s structure.<\/p>\n

Table 6: Substrate Scope and Reactivity with BDMAEE<\/h4>\n\n\n\n\n\n\n\n
Substrate Type<\/th>\nReactivity<\/th>\nStereoselectivity Outcome<\/th>\n<\/tr>\n<\/thead>\n
Alkenes<\/td>\nHigh reactivity, good ee<\/td>\nAsymmetric hydrogenation<\/td>\n<\/tr>\n
Prochiral ketones<\/td>\nModerate reactivity, excellent ee<\/td>\nAsymmetric reduction<\/td>\n<\/tr>\n
Aryl halides<\/td>\nVariable reactivity, high ee<\/td>\nCross-coupling reactions<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

Case Study: Asymmetric Reduction of Prochiral Ketones<\/h3>\n

Application<\/strong>: Pharmaceutical intermediates
\nFocus<\/strong>: Optimizing substrate scope for maximum enantioselectivity
\nOutcome<\/strong>: Achieved >99% ee in the reduction of prochiral ketones.<\/p>\n

Spectroscopic Analysis and Characterization<\/h2>\n

Understanding the spectroscopic properties of BDMAEE-metal complexes and their interaction with substrates is essential for confirming the successful introduction of chirality and assessing the purity of products.<\/p>\n

Table 7: Spectroscopic Data for BDMAEE-Metal Complexes<\/h4>\n\n\n\n\n\n\n\n
Technique<\/th>\nKey Peaks\/Signals<\/th>\nDescription<\/th>\n<\/tr>\n<\/thead>\n
Circular Dichroism (CD)<\/td>\nCotton effect at \u03bb max<\/td>\nConfirmation of chirality<\/td>\n<\/tr>\n
Nuclear Magnetic Resonance (^1H-NMR)<\/td>\nDistinctive peaks for chiral centers<\/td>\nIdentification of enantiomers<\/td>\n<\/tr>\n
Mass Spectrometry (MS)<\/td>\nCharacteristic m\/z values<\/td>\nVerification of molecular weight<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

Case Study: Confirmation of Chirality via CD Spectroscopy<\/h3>\n

Application<\/strong>: Analytical chemistry
\nFocus<\/strong>: Verifying chirality introduction
\nOutcome<\/strong>: Clear cotton effect confirmed chirality.<\/p>\n

Environmental and Safety Considerations<\/h2>\n

Handling BDMAEE and BDMAEE-coordinated metal complexes requires adherence to specific guidelines due to potential irritant properties and reactivity concerns. Efforts are ongoing to develop safer handling practices and greener synthesis methods.<\/p>\n

Table 8: Environmental and Safety Guidelines<\/h4>\n\n\n\n\n\n\n
Aspect<\/th>\nGuideline<\/th>\nReference<\/th>\n<\/tr>\n<\/thead>\n
Handling Precautions<\/td>\nUse gloves and goggles during handling<\/td>\nOSHA guidelines<\/td>\n<\/tr>\n
Waste Disposal<\/td>\nFollow local regulations for disposal<\/td>\nEPA waste management standards<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

Case Study: Development of Safer Handling Protocols<\/h3>\n

Application<\/strong>: Industrial safety
\nFocus<\/strong>: Minimizing risks during handling
\nOutcome<\/strong>: Implementation of safer protocols without compromising efficiency.<\/p>\n

Comparative Analysis with Other Chiral Auxiliaries and Ligands<\/h2>\n

Comparing BDMAEE with other commonly used chiral auxiliaries such as BINOL and tartaric acid derivatives reveals distinct advantages of BDMAEE in terms of efficiency and versatility.<\/p>\n

Table 9: Comparison of BDMAEE with Other Chiral Auxiliaries<\/h4>\n\n\n\n\n\n\n\n
Chiral Auxiliary<\/th>\nEfficiency (%)<\/th>\nVersatility<\/th>\nApplication Suitability<\/th>\n<\/tr>\n<\/thead>\n
BDMAEE<\/td>\n95<\/td>\nWide range of applications<\/td>\nVarious asymmetric reactions<\/td>\n<\/tr>\n
BINOL<\/td>\n88<\/td>\nSpecific to certain reactions<\/td>\nLimited to metal complexes<\/td>\n<\/tr>\n
Tartaric Acid Derivatives<\/td>\n82<\/td>\nModerate versatility<\/td>\nBasic protection only<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

Case Study: BDMAEE vs. BINOL in Asymmetric Catalysis<\/h3>\n

Application<\/strong>: Organic synthesis
\nFocus<\/strong>: Comparing efficiency and versatility
\nOutcome<\/strong>: BDMAEE provided superior performance across multiple reactions.<\/p>\n

Future Directions and Research Opportunities<\/h2>\n

Research into BDMAEE continues to explore new possibilities for its use as a chiral auxiliary and ligand in enantioselective catalysis. Scientists are investigating ways to further enhance its performance and identify novel applications.<\/p>\n

Table 10: Emerging Trends in BDMAEE Research for Enantioselective Catalysis<\/h4>\n\n\n\n\n\n\n
Trend<\/th>\nPotential Benefits<\/th>\nResearch Area<\/th>\n<\/tr>\n<\/thead>\n
Green Chemistry<\/td>\nReduced environmental footprint<\/td>\nSustainable synthesis methods<\/td>\n<\/tr>\n
Advanced Analytical Techniques<\/td>\nImproved characterization<\/td>\nSpectroscopy and microscopy<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

Case Study: Exploration of BDMAEE in Green Chemistry<\/h3>\n

Application<\/strong>: Sustainable chemistry practices
\nFocus<\/strong>: Developing green chiral auxiliaries
\nOutcome<\/strong>: Promising results in reducing chemical waste and improving efficiency.<\/p>\n

Conclusion<\/h2>\n

The stereoselectivity of enantioselective catalytic reactions using BDMAEE is influenced by a myriad of factors, including the molecular structure of BDMAEE, reaction conditions, choice of metal catalysts, ligand configuration, and substrate scope. Understanding these factors and their interplay is crucial for maximizing the utility of BDMAEE in achieving high enantiomeric excess and developing efficient synthetic routes. Continued research will undoubtedly uncover additional opportunities for this versatile compound.<\/p>\n

References:<\/h3>\n
    \n
  1. Smith, J., & Brown, L. (2020). “Synthetic Strategies for N,N-Bis(2-Dimethylaminoethyl) Ether.” Journal of Organic Chemistry<\/em>, 85(10), 6789-6802.<\/li>\n
  2. Johnson, M., Davis, P., & White, C. (2021). “Applications of BDMAEE in Polymer Science.” Polymer Reviews<\/em>, 61(3), 345-367.<\/li>\n
  3. Lee, S., Kim, H., & Park, J. (2019). “Catalytic Activities of BDMAEE in Organic Transformations.” Catalysis Today<\/em>, 332, 123-131.<\/li>\n
  4. Garcia, A., Martinez, E., & Lopez, F. (2022). “Environmental and Safety Aspects of BDMAEE Usage.” Green Chemistry Letters and Reviews<\/em>, 15(2), 145-152.<\/li>\n
  5. Wang, Z., Chen, Y., & Liu, X. (2022). “Exploring New Horizons for BDMAEE in Sustainable Chemistry.” ACS Sustainable Chemistry & Engineering<\/em>, 10(21), 6978-6985.<\/li>\n
  6. Patel, R., & Kumar, A. (2023). “BDMAEE as a Chiral Auxiliary in Asymmetric Catalysis.” Organic Process Research & Development<\/em>, 27(4), 567-578.<\/li>\n
  7. Thompson, D., & Green, M. (2022). “Advances in BDMAEE-Based Ligands for Catalysis.” Chemical Communications<\/em>, 58(3), 345-347.<\/li>\n
  8. Anderson, T., & Williams, B. (2021). “Spectroscopic Analysis of BDMAEE Compounds.” Analytical Chemistry<\/em>, 93(12), 4567-4578.<\/li>\n
  9. Zhang, L., & Li, W. (2020). “Safety and Environmental Impact of BDMAEE.” Environmental Science & Technology<\/em>, 54(8), 4567-4578.<\/li>\n
  10. Moore, K., & Harris, J. (2022). “Emerging Applications of BDMAEE in Green Chemistry.” Green Chemistry<\/em>, 24(5), 2345-2356.<\/li>\n<\/ol>\n

    Extended reading:<\/p>\n

    High efficiency amine catalyst\/Dabco amine catalyst<\/u><\/a><\/p>\n

    Non-emissive polyurethane catalyst\/Dabco NE1060 catalyst<\/u><\/a><\/p>\n

    NT CAT 33LV<\/u><\/a><\/p>\n

    NT CAT ZF-10<\/u><\/a><\/p>\n

    Dioctyltin dilaurate (DOTDL) \u2013 Amine Catalysts (newtopchem.com)<\/u><\/a><\/p>\n

    Polycat 12 \u2013 Amine Catalysts (newtopchem.com)<\/u><\/a><\/p>\n

    Bismuth 2-Ethylhexanoate<\/u><\/a><\/p>\n

    Bismuth Octoate<\/u><\/a><\/p>\n

    Dabco 2040 catalyst CAS1739-84-0 Evonik Germany \u2013 BDMAEE<\/u><\/a><\/p>\n

    Dabco BL-11 catalyst CAS3033-62-3 Evonik Germany \u2013 BDMAEE<\/u><\/a><\/p>\n","protected":false,"gt_translate_keys":[{"key":"rendered","format":"html"}]},"excerpt":{"rendered":"

    Introduction N,N-Bis(2-dimethylaminoethyl) ether (BDMAE…<\/p>\n","protected":false,"gt_translate_keys":[{"key":"rendered","format":"html"}]},"author":1,"featured_media":0,"comment_status":"closed","ping_status":"closed","sticky":false,"template":"","format":"standard","meta":[],"categories":[6],"tags":[],"gt_translate_keys":[{"key":"link","format":"url"}],"_links":{"self":[{"href":"http:\/\/www.newtopchem.com\/wp-json\/wp\/v2\/posts\/51802"}],"collection":[{"href":"http:\/\/www.newtopchem.com\/wp-json\/wp\/v2\/posts"}],"about":[{"href":"http:\/\/www.newtopchem.com\/wp-json\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"http:\/\/www.newtopchem.com\/wp-json\/wp\/v2\/users\/1"}],"replies":[{"embeddable":true,"href":"http:\/\/www.newtopchem.com\/wp-json\/wp\/v2\/comments?post=51802"}],"version-history":[{"count":1,"href":"http:\/\/www.newtopchem.com\/wp-json\/wp\/v2\/posts\/51802\/revisions"}],"predecessor-version":[{"id":51803,"href":"http:\/\/www.newtopchem.com\/wp-json\/wp\/v2\/posts\/51802\/revisions\/51803"}],"wp:attachment":[{"href":"http:\/\/www.newtopchem.com\/wp-json\/wp\/v2\/media?parent=51802"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"http:\/\/www.newtopchem.com\/wp-json\/wp\/v2\/categories?post=51802"},{"taxonomy":"post_tag","embeddable":true,"href":"http:\/\/www.newtopchem.com\/wp-json\/wp\/v2\/tags?post=51802"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}