FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2321059743> ?p ?o ?g. }

• W2321059743 endingPage "1355" @default.
• W2321059743 startingPage "1345" @default.
• W2321059743 abstract "Chiral diamines are important building blocks for constructing stereoselective catalysts, including transition metal based catalysts and organocatalysts that facilitate oxidation, reduction, hydrolysis, and C–C bond forming reactions. These molecules are also critical components in the synthesis of drugs, including antiviral agents such as Tamiflu and Relenza and anticancer agents such as oxaliplatin and nutlin-3. The diaza-Cope rearrangement reaction provides one of the most versatile methods for rapidly generating a wide variety of chiral diamines stereospecifically and under mild conditions. Weak forces such as hydrogen bonding, electronic, steric, oxyanionic, and conjugation effects can drive this equilibrium process to completion.In this Account, we examine the effect of these individual weak forces on the value of the equilibrium constant for the diaza-Cope rearrangement reaction using both computational and experimental methods. The availability of a wide variety of aldehydes and diamines allows for the facile synthesis of the diimines needed to study the weak forces. Furthermore, because the reaction generally takes place cleanly at ambient temperature, we can easily measure equilibrium constants for rearrangement of the diimines. We use the Hammett equation to further examine the electronic and oxyanionic effects. In addition, computations and experiments provide us with new insights into the origin and extent of stereospecificity for this rearrangement reaction.The diaza-Cope rearrangement, with its unusual interplay between weak forces and the equilibrium constant of the reaction, provides a rare opportunity to study the effects of the fundamental weak forces on a chemical reaction. Among these many weak forces that affect the diaza-Cope rearrangement, the anion effect is the strongest (10.9 kcal/mol) followed by the resonance-assisted hydrogen-bond effect (7.1 kcal/mol), the steric effect (5.7 kcal/mol), the conjugation effect (5.5 kcal/mol), and the electronic effect (3.2 kcal/mol). Based on both computation and experimental data, the effects of these weak forces are additive. Understanding the interplay of the weak forces in the [3,3]-sigmatropic reaction is interesting in its own right and also provides valuable insights for the synthesis of chiral diamine based drugs and catalysts in excellent yield and enantiopurity." @default.
• W2321059743 created "2016-06-24" @default.
• W2321059743 creator A5008383067 @default.
• W2321059743 creator A5012929329 @default.
• W2321059743 creator A5077185233 @default.
• W2321059743 creator A5085447652 @default.
• W2321059743 date "2012-06-07" @default.
• W2321059743 modified "2023-09-27" @default.
• W2321059743 title "Understanding the Interplay of Weak Forces in [3,3]-Sigmatropic Rearrangement for Stereospecific Synthesis of Diamines" @default.
• W2321059743 cites W196915156 @default.
• W2321059743 cites W1971799292 @default.
• W2321059743 cites W1980864184 @default.
• W2321059743 cites W2000449378 @default.
• W2321059743 cites W2005729036 @default.
• W2321059743 cites W2008111544 @default.
• W2321059743 cites W2009032195 @default.
• W2321059743 cites W2012404011 @default.
• W2321059743 cites W2012722108 @default.
• W2321059743 cites W2012909581 @default.
• W2321059743 cites W2013160605 @default.
• W2321059743 cites W2016268293 @default.
• W2321059743 cites W2016625343 @default.
• W2321059743 cites W2028646034 @default.
• W2321059743 cites W2029225706 @default.
• W2321059743 cites W2030165061 @default.
• W2321059743 cites W2032643359 @default.
• W2321059743 cites W2042635510 @default.
• W2321059743 cites W2055980669 @default.
• W2321059743 cites W2061377061 @default.
• W2321059743 cites W2062347718 @default.
• W2321059743 cites W2063966085 @default.
• W2321059743 cites W2064116691 @default.
• W2321059743 cites W2068345926 @default.
• W2321059743 cites W2070423225 @default.
• W2321059743 cites W2078708616 @default.
• W2321059743 cites W2084699035 @default.
• W2321059743 cites W2095418067 @default.
• W2321059743 cites W2097933346 @default.
• W2321059743 cites W2109574023 @default.
• W2321059743 cites W2116393429 @default.
• W2321059743 cites W2144512481 @default.
• W2321059743 cites W2158565858 @default.
• W2321059743 cites W2160790360 @default.
• W2321059743 cites W2165637693 @default.
• W2321059743 cites W2298119074 @default.
• W2321059743 cites W2314076703 @default.
• W2321059743 cites W2315016671 @default.
• W2321059743 cites W2330038549 @default.
• W2321059743 cites W2484208220 @default.
• W2321059743 cites W3005194507 @default.
• W2321059743 cites W46105479 @default.
• W2321059743 doi "https://doi.org/10.1021/ar2002842" @default.
• W2321059743 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/22676401" @default.
• W2321059743 hasPublicationYear "2012" @default.
• W2321059743 type Work @default.
• W2321059743 sameAs 2321059743 @default.
• W2321059743 citedByCount "34" @default.
• W2321059743 countsByYear W23210597432012 @default.
• W2321059743 countsByYear W23210597432013 @default.
• W2321059743 countsByYear W23210597432014 @default.
• W2321059743 countsByYear W23210597432015 @default.
• W2321059743 countsByYear W23210597432016 @default.
• W2321059743 countsByYear W23210597432017 @default.
• W2321059743 countsByYear W23210597432018 @default.
• W2321059743 countsByYear W23210597432019 @default.
• W2321059743 countsByYear W23210597432020 @default.
• W2321059743 countsByYear W23210597432021 @default.
• W2321059743 countsByYear W23210597432022 @default.
• W2321059743 countsByYear W23210597432023 @default.
• W2321059743 crossrefType "journal-article" @default.
• W2321059743 hasAuthorship W2321059743A5008383067 @default.
• W2321059743 hasAuthorship W2321059743A5012929329 @default.
• W2321059743 hasAuthorship W2321059743A5077185233 @default.
• W2321059743 hasAuthorship W2321059743A5085447652 @default.
• W2321059743 hasConcept C10710636 @default.
• W2321059743 hasConcept C147597530 @default.
• W2321059743 hasConcept C147789679 @default.
• W2321059743 hasConcept C161790260 @default.
• W2321059743 hasConcept C178790620 @default.
• W2321059743 hasConcept C181647583 @default.
• W2321059743 hasConcept C185592680 @default.
• W2321059743 hasConcept C187921627 @default.
• W2321059743 hasConcept C201194858 @default.
• W2321059743 hasConcept C21951064 @default.
• W2321059743 hasConcept C32909587 @default.
• W2321059743 hasConcept C58590140 @default.
• W2321059743 hasConcept C89031862 @default.
• W2321059743 hasConceptScore W2321059743C10710636 @default.
• W2321059743 hasConceptScore W2321059743C147597530 @default.
• W2321059743 hasConceptScore W2321059743C147789679 @default.
• W2321059743 hasConceptScore W2321059743C161790260 @default.
• W2321059743 hasConceptScore W2321059743C178790620 @default.
• W2321059743 hasConceptScore W2321059743C181647583 @default.
• W2321059743 hasConceptScore W2321059743C185592680 @default.
• W2321059743 hasConceptScore W2321059743C187921627 @default.
• W2321059743 hasConceptScore W2321059743C201194858 @default.
• W2321059743 hasConceptScore W2321059743C21951064 @default.
• W2321059743 hasConceptScore W2321059743C32909587 @default.

• next