Tandem Aldol Reaction from Acetal Mixtures by an Artificial Enzyme with Site-Isolated Acid and Base Functionalities

2021 ◽  
Author(s):  
Ishani Bose ◽  
Yan Zhao
Keyword(s):  
Aldol Reaction ◽  
Artificial Enzyme ◽  
Acid And Base

TEM visualization of surface replicated acid and base catalyzed sol-gel glasses

1986 ◽  
Vol 44 ◽  
pp. 448-449
Author(s):  
George C. Ruben ◽  
Merrill W. Shafer
Keyword(s):  
Elevated Temperatures ◽  
Sol Gel ◽  
Basic Medium ◽  
Glass Transition Point ◽  
Structural Space ◽  
Acid And Base ◽  
Organometallic Precursors ◽  
New Processing ◽  
Gel Glasses ◽  
Physical Phenomena

Traditionally ceramics have been shaped from powders and densified at temperatures close to their liquid point. New processing methods using various types of sols, gels, and organometallic precursors at low temperature which enable densificatlon at elevated temperatures well below their liquidus, hold the promise of producing ceramics and glasses of controlled and reproducible properties that are highly reliable for electronic, structural, space or medical applications. Ultrastructure processing of silicon alkoxides in acid medium and mixtures of Ludox HS-40 (120Å spheres from DuPont) and Kasil (38% K2O &62% SiO2) in basic medium have been aimed at producing materials with a range of well defined pore sizes (∼20-400Å) to study physical phenomena and materials behavior in well characterized confined geometries. We have studied Pt/C surface replicas of some of these porous sol-gels prepared at temperatures below their glass transition point.

An Alternate Energy-Conserved Pathway for the Morita-Baylis-Hillman (MBH) Reaction

2020 ◽  
Author(s):  
Veejendra Yadav
Keyword(s):  
Proton Transfer ◽  
Transition State ◽  
Lower Energy ◽  
Aldol Reaction ◽  
Membered Ring ◽  
Ammonium Ion ◽  
Alternate Energy ◽  
Ring Transition State ◽  
Mbh Reaction

An new overall lower energy pathway for the amine-catalysed Morita-Baylis-Hillman reaction is proposed from computations at the M06-2X/6-311++G(d,p) level. The pathway involves proton-transfer from the ammonium ion to the alkoxide formed from the aldol reaction through a seven-membered ring transition state (TS) structure followed by highly exothermic Hofmann<i> </i>elimination through a five-membered ring TS structure to form the product and also release the catalyst to carry on with the process all over again.

An Alternate Energy-Conserved Pathway for the Morita-Baylis-Hillman (MBH) Reaction

2020 ◽  
Author(s):  
Veejendra Yadav
Keyword(s):  
Proton Transfer ◽  
Transition State ◽  
Lower Energy ◽  
Aldol Reaction ◽  
Membered Ring ◽  
Ammonium Ion ◽  
Alternate Energy ◽  
Ring Transition State ◽  
Mbh Reaction

An new overall lower energy pathway for the amine-catalysed Morita-Baylis-Hillman reaction is proposed from computations at the M06-2X/6-311++G(d,p) level. The pathway involves proton-transfer from the ammonium ion to the alkoxide formed from the aldol reaction through a seven-membered ring transition state (TS) structure followed by highly exothermic Hofmann<i> </i>elimination through a five-membered ring TS structure to form the product and also release the catalyst to carry on with the process all over again.

Mukaiyama Aldol Reaction Catalyzed by (Benz)imidazolium-Based Halogen Bond Donors

2020 ◽  
Author(s):  
Revannath L. Sutar ◽  
Nikita Erochok ◽  
Stefan Huber
Keyword(s):  
Halogen Bond ◽  
Aldol Reaction ◽  
Mukaiyama Aldol Reaction ◽  
Mukaiyama Aldol ◽  
Background Reaction ◽  
Strong Performance ◽  
The Stability ◽  
Elemental Iodine

A series of cationic monodentate and bidentate iodo(benz)­imidazolium-based halogen bond (XB) donors were employed as catalysts in a Mukaiyama aldol reaction. While 5 mol% of a monodentate variant showed noticeable activity, a <i>syn</i>-preorganized bidentate XB donor provided a strong performance even with 0.5 mol% loading. In contrast to the very active BAr<sup>F</sup><sub>4</sub> salts, PF<sub>6</sub> or OTf salts were either inactive or showed background reaction. Repetition experiments clearly ruled out a potential hidden catalysis by elemental iodine and demonstrated the stability of our catalyst over three consecutive cycles.

Synthesis of the C19–C30 Bis-THF Fragment of Iriomoteolide-13a via Stepwise SN2 Cyclization and Intramolecular syn-Oxypalladation

2020 ◽  
Author(s):  
Hui Zhao ◽  
Kai Gao ◽  
Haichen Ma ◽  
Tsz Chun Yip ◽  
Wei-Min Dai
Keyword(s):  
Aldol Reaction ◽  
Allylic Alcohol ◽  
Asymmetric Dihydroxylation ◽  
Hydroxy Groups

The C19–C30 bis-THF fragment of the proposed structure of iriomoteolide-13a has been synthesized. The w-mesyloxy-substituted stereotetrad possessing three continuous hydroxy groups was generated by <i>anti</i>-aldol reaction and asymmetric dihydroxylation (AD). Upon heating in pyridine the stereotetrad underwent an S<sub>N</sub>2 cyclization to form the C19–C22 THF ring. It was followed by an intramolecular <i>syn</i>-oxypalladation of the C28 chiral allylic alcohol to give the C23–C26 THF ring.

Fe-N-C Artificial Enzyme: Activation of Oxygen for Dehydrogenation and Monoxygenation of Organic Substrates under Mild Condition and Cancer Therapeutic Application

2018 ◽  
Author(s):  
Fei He ◽  
Li Mi ◽  
Yanfei Shen ◽  
Toshiyuki Mori ◽  
Songqin Liu ◽  
...  
Keyword(s):  
Mild Condition ◽  
Enzyme Activation ◽  
Artificial Enzymes ◽  
Organic Substrates ◽  
Artificial Enzyme ◽  
Therapeutic Application ◽  
Highly Efficient ◽  
Activation Of Oxygen

Developing highly efficient artificial enzymes that directly employ O<sub>2</sub> as terminal oxidant has long been pursued but has rarely achieved yet. We report Fe-N-C has unusual enzyme-like activity in both dehydrogenation and monoxygenation of organic substrates with ~100% selectivity by direct using O<sub>2</sub>.

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