Fragmentation of cyclobutoxychlorocarbene: the cyclopropylcarbinyl/cyclobutyl cations revisited

Moss, Robert A.; Zheng, Fenping; Johnson, Lauren A.; Sauers, Ronald R.

doi:10.1002/poc.371

Cited by 14 publications

(28 citation statements)

References 24 publications

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“…The migrating carbons of the transition structures for 9 and 10 lie midway along the reaction coordinates in contrast to the "early" transition structures computed for the cyclopropylmethyl analogue 34 (E a ) 3.0 kcal/mol) and the 1-adamantylmethyl system 5,8 (E a ) 5.6 kcal/mol). Whereas strain relief provides a significant driving force for the 1-norbornylmethyl rearrangements, strain increases for the 1-adamantylmethyl rearrangement.…”

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confidence: 71%

The Carbene Fragmentation−Ring Expansion Route to Bridgehead Carbocations

et al. 2002

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[reaction: see text]The products, kinetics, and activation parameters were determined for the fragmentation-ring expansions of 1-norbornylmethyloxychlorocarbene (11) and 3-noradamantylmethyloxychlorocarbene (17). Products from 11 (in dichloroethane) included 1-chlorobicyclo[2.2.2]octane (9, 56%) and 1-chlorobicyclo[3.2.1]octane (10, 37%); from 17, we obtained 1-chloroadamantane (15, 68%) and protoadamantyl chloride (16, 28%).

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confidence: 71%

The Carbene Fragmentation−Ring Expansion Route to Bridgehead Carbocations

et al. 2002

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“…Both allylic and cyclopropylcarbinyl compounds − undergo S N 1 reactions at accelerated rates via allylic and nonclassical bicyclobutonium cationic intermediates, , respectively. Of note, distinct conformations are required for formation of delocalized carbocations from inhibitors 2 and 3 .…”

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confidence: 99%

New Class of Glycoside Hydrolase Mechanism-Based Covalent Inhibitors: Glycosylation Transition State Conformations

et al. 2017

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The design of covalent inhibitors in glycoscience research is important for the development of chemical biology probes. Here we report the synthesis of a new carbocyclic mechanism-based covalent inhibitor of an α-glucosidase. The enzyme efficiently catalyzes its alkylation via either an allylic cation or a cationic transition state. We show this allylic covalent inhibitor has different catalytic proficiencies for pseudoglycosylation and deglycosylation. Such inhibitors have the potential to be useful chemical biology tools.

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“…A mechanism‐based covalent inhibitor is a compound that, bearing a structural similarity to an enzymatic substrate and also a reactive functionality, results in direct covalent binding to the enzyme and thus to its inactivation. Cyclopropyl rings have been explored in this context, because their strained σ‐bonds can stabilize discrete cationic species generated under catalysis of GHs, yielding cationic intermediates which covalently trap catalytically relevant nucleophiles in the enzyme active site. Chakladar et al designed two bicyclo[4.1.0]heptyl analogues of galactose ( 38 and 39 ; Figure A) containing the cyclopropyl moiety and targeted against retaining α‐galactosidases.…”

Section: Endocyclic Oxygen Replacementmentioning

confidence: 99%

Design and synthesis of glycomimetics: Recent advances

Tamburrini

Colombo

Bernardi

2019

Medicinal Research Reviews

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In the past few decades, our understanding of glycan information‐encoding power has notably increased, thus leading to a significant growth also in the design and synthesis of glycomimetic probes. Combining data from multiple analytical sources, such as crystallography, nuclear magnetic resonance spectroscopy, and other biophysical methods (eg, surface plasmon resonance and carbohydrate microarrays) has allowed to shed light on the key interaction events between carbohydrates and their protein‐targets. However, the low metabolic stability of carbohydrates and their high hydrophilicity, which translates in low bioavailability, undermine their development as drugs. In this framework, the design of chemically modified analogues (called carbohydrate mimics or glycomimetics) appears as a valid alternative for the development of therapeutic agents. Glycomimetics, as structural and functional mimics of carbohydrates, can replace the native ligands in the interaction with target proteins, but are designed to show enhanced enzymatic stability and bioavailability and, possibly, an improved affinity and selectivity toward the target. In the present account, we specifically focus on the most recent advances in the design and synthesis of glycomimetics. In particular, we highlight the efforts of the scientific community in the development of straightforward synthetic procedures for the preparation of sugar mimics and in their preliminary biological evaluation.

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Fragmentation of cyclobutoxychlorocarbene: the cyclopropylcarbinyl/cyclobutyl cations revisited

Cited by 14 publications

References 24 publications

The Carbene Fragmentation−Ring Expansion Route to Bridgehead Carbocations

The Carbene Fragmentation−Ring Expansion Route to Bridgehead Carbocations

New Class of Glycoside Hydrolase Mechanism-Based Covalent Inhibitors: Glycosylation Transition State Conformations

Design and synthesis of glycomimetics: Recent advances

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