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Several recent studies have also examined the chemistry of superelectrophilic fluorenyl cations. The fluorenyl cation itself is expected to be a reactive cation due to its weak anti-aromatic character. Mills and coworkers examined the first dicationic fluorenyl cations and noted their instability [26,27,28]. Our group developed an efficient route to 9,9-diarylfluorenes through a superacid-promoted cyclization (Scheme 7) [29,30]. For example, the pyrazine derivative 24 undergoes reaction in superacid with benzene to give the 9,9-diarylfluorene product 28 in 91% yield. The cyclization step is thought to involve the tricationic carboxonium (25) as the intermediate leading to the new carbocycle. Dehydration through the oxonium ion 26 leads to the highly electrophilic fluorenyl ion 27. This tricationic species has been directly observed by low temperature NMR using stable ion conditions [31]. Reaction with benzene gives 28 as the final product. The condensation chemistry was also adapted to a polymer synthesis wherein the fluorene ring system is part of the polymer backbone [30].
A novel series of spirocyclic diazafluorene products have been prepared from superelectrophilic reactions with phenols [33]. For example, the diazafluorenone undergoes condensation with 4-methylphenol to give the spirocyclic product 32 in excellent yield (Scheme 9). The mechanism involves a multiply protonated diazafluorenone, initially a superelectrophilic carboxonium ion (33). Our own experience with these types of systems has indicated that N-deprotonation can occur with highly charge structures such as superelectrophile 33 (giving a dicationic superelectrophile). Electrophilic aromatic substitution and elimination of water then leads to a charge-delocalized, superelectrophilic carbocation (34). As indicated by the resonance structure, the ion generates considerable positive charge on the phenol ring and this leads to nucleophilic attack at the phenol ring carbon to provide intermediate 35. Subsequent steps give dehydration and ring formation to give the final product. Control experiments demonstrated that formation of the biaryl ether structure does not occur by the condensation of two phenols, but rather this structure is formed sequentially at the aza-fluorene ring.
A similar observation was made by this same research group in their study of a superelectrophilic Nazarov cyclization [61]. Thus, diprotonation of the propenone derivative 66 leads to the Nazarov product 67 (Scheme 17). Kinetic studies and theoretical calculations provided strong evidence for the involvement of superelectrophile 68, where double protonation at the carbonyl oxygen leads to this key intermediate.
Interestingly, Ohwada and coworkers described a similar cyclization with carbamoyl salicylates [74]. For example, compound 113 reacts rapidly in triflic acid (10 equivalents) to provide the heterocyclic product 114 in excellent yield (Scheme 25). NMR studies of this system revealed that a diprotonated species (117) may be formed in superacid. However, kinetic studies showed that increasing media acidity was accompanied by lower reaction rates and increasing activation parameters. This suggested that cleavage to the protonated isocyanate intermediate116 occurs better through the monoprotonated species 115, as the dicationic species 117 is more stable towards cleavage. A companion study from the same group showed that methyl carbamates also provided the cyclization products (i.e., 114) in superacidic media [75]. In this case, kinetic studies showed increasing rates of cyclization with increasing superacid strength. Diprotonated, superlectrophilic intermediates were suggested for this cyclization.
Other dicarbonyl compounds have been utilized in synthetic methods with superelectrophiles. For example, Ohwada and coworkers examined the superacid-promoted cyclizations of a series of β-ketoesters and related systems and superelectrophiles were proposed as intermediates (Scheme 28) [84]. Thus, compound 128 reacts in excess of triflic acid (10 equivalents) to provide the indene 129 in 88% yield as a mixture of ester and acid products (72:28 ratio; Scheme 28). NMR studies indicate that the β-ketoesters are diprotonated at the carbonyl groups (130) at an acid strength of Ho -11. In kinetic studies, it was observed that the cyclization rate increased linearly with acid strengths above Ho -11.
Antivirus software was originally developed to detect and remove computer viruses, hence the name. However, with the proliferation of other malware, antivirus software started to protect against other computer threats. Some products also include protection from malicious URLs, spam, and phishing.[1]
There are competing claims for the innovator of the first antivirus product. Possibly, the first publicly documented removal of an \"in the wild\" computer virus (i.e. the \"Vienna virus\") was performed by Bernd Fix in 1987.[19][20]
In 1987, Andreas Lüning and Kai Figge, who founded G Data Software in 1985, released their first antivirus product for the Atari ST platform.[21] In 1987, the Ultimate Virus Killer (UVK) was also released.[22] This was the de facto industry standard virus killer for the Atari ST and Atari Falcon, the last version of which (version 9.0) was released in April 2004.[citation needed] In 1987, in the United States, John McAfee founded the McAfee company (was part of Intel Security[23]) and, at the end of that year, he released the first version of VirusScan.[24] Also in 1987 (in Czechoslovakia), Peter Paško, Rudolf Hrubý, and Miroslav Trnka created the first version of NOD antivirus.[25][26]
In the end of the 1980s, in United Kingdom, Jan Hruska and Peter Lammer founded the security firm Sophos and began producing their first antivirus and encryption products. In the same period, in Hungary, also VirusBuster was founded (which has recently being incorporated by Sophos).
On the basis that Norton/Symantec has done this for every one of the last three releases of Pegasus Mail, we can only condemn this product as too flawed to use, and recommend in the strongest terms that our users cease using it in favour of alternative, less buggy anti-virus packages.[110]
Support issues also exist around antivirus application interoperability with common solutions like SSL VPN remote access and network access control products.[129] These technology solutions often have policy assessment applications that require an up-to-date antivirus to be installed and running. If the antivirus application is not recognized by the policy assessment, whether because the antivirus application has been updated or because it is not part of the policy assessment library, the user will be unable to connect.
It's something that they miss a lot of the time because this type of [ransomware virus] comes from sites that use a polymorphism, which means they basically randomize the file they send you and it gets by well-known antivirus products very easily. I've seen people firsthand getting infected, having all the pop-ups and yet they have antivirus software running and it's not detecting anything. It actually can be pretty hard to get rid of, as well, and you're never really sure if it's really gone. When we see something like that usually we advise to reinstall the operating system or reinstall backups.[138]
Antivirus software itself usually runs at the highly trusted kernel level of the operating system to allow it access to all the potential malicious process and files, creating a potential avenue of attack.[152] The US National Security Agency (NSA) and the UK Government Communications Headquarters (GCHQ) intelligence agencies, respectively, have been exploiting anti-virus software to spy on users.[153] Anti-virus software has highly privileged and trusted access to the underlying operating system, which makes it a much more appealing target for remote attacks.[154] Additionally anti-virus software is \"years behind security-conscious client-side applications like browsers or document readers. It means that Acrobat Reader, Microsoft Word or Google Chrome are harder to exploit than 90 percent of the anti-virus products out there\", according to Joxean Koret, a researcher with Coseinc, a Singapore-based information security consultancy.[154]
S3P treatments involve low temperature diffusion of large quantities of carbon and/or nitrogen into the surface without the formation of chromium precipitations. No additional chemical elements that were not already present prior to the treatment are introduced during the process. There is no risk of delamination because S3P processes neither add a coating nor introduce brittle phases in the material.
Abstract:Superelectrophiles are reactive species that often carry multiple positive charges. They have been useful in numerous synthetic methods and they often exhibit highly unusual reactivities. Recent advances in superelectrophile chemistry are discussed in this review.Keywords: superelectrophiles; superacid; trifluoromethanesulfonic acid; protonation; protosolvation; dications; C-H activation; anti-Markovnikov addition
In all rearrangements of 1,6-enynes 1 (Fig. 3), the substitution pattern on the olefin will have a major influence on the stability of carbocation intermediate 5 and susceptibility of the cyclopropane ring in intermediate 6 to nucleophilic attack. Thus, we reasoned that increasing the stability of the intermediary carbocation might open paths to different rearrangements and scaffolds. To explore this notion, dimethyl substituted enynes 13 were exposed to different gold complexes, and gratifyingly treatment with highly electrophilic gold complex II in DCM selectively yielded structurally different df-oxindoles 14. Solvent variation (Supplementary Table 2) revealed that in tetrahydrofuran product 14a was formed in almost quantitative yield as a single diastereoisomer (Fig. 4). 153554b96e
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