First synthesis of 3,3-difluoroserine and cysteine derivatives via Mg(0)-promoted selective CF bond cleavage of trifluoromethylimines

Mae, Masayuki; Amii, Hideki; Uneyama, Kenji

doi:10.1016/s0040-4039(00)01350-2

Cited by 76 publications

(37 citation statements)

References 23 publications

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“…Fluorinated analogues of protected serine and cysteine have been synthesized. 172 However, the free analogues are unstable and peptides containing these residues have, to the best of our knowledge, never been reported. of glutamic acid using the tripeptide (Boc-Xaa-Glu-[ 3 H]Val).…”

Section: Analogues Of Polar and Charged Amino Acids 41 General Propementioning

confidence: 94%

Fluorinated amino acids: compatibility with native protein structures and effects on protein–protein interactions

et al. 2012

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Fluorinated analogues of the canonical α-L-amino acids have gained widespread attention as building blocks that may endow peptides and proteins with advantageous biophysical, chemical and biological properties. This critical review covers the literature dealing with investigations of peptides and proteins containing fluorinated analogues of the canonical amino acids published over the course of the past decade including the late nineties. It focuses on side-chain fluorinated amino acids, the carbon backbone of which is identical to their natural analogues. Each class of amino acids--aliphatic, aromatic, charged and polar as well as proline--is presented in a separate section. General effects of fluorine on essential properties such as hydrophobicity, acidity/basicity and conformation of the specific side chains and the impact of these altered properties on stability, folding kinetics and activity of peptides and proteins are discussed (245 references).

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Section: Analogues Of Polar and Charged Amino Acids 41 General Propementioning

confidence: 94%

Fluorinated amino acids: compatibility with native protein structures and effects on protein–protein interactions

et al. 2012

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“…Difluoromethyl ketimine 5 was prepared from trifluoromethyl ketimine 3 (Scheme ). The carbon–fluorine bond was reductively cleaved by magnesium to form N ‐trimethylsilyl enamine 4 , according to Uneyama and co‐workers’ method,9 and subsequent treatment of 4 with tetrabutylammonium fluoride gave difluoromethyl ketimine 5 a in good yield as an inseparable mixture of E / Z isomers (ca. 2:1, determined by 1 H and 19 F NMR spectroscopy).…”

Section: Resultsmentioning

confidence: 99%

Shale Gas Technology: A Special Issue

Veser

2014

Energy Tech

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No other development since the "oil shock" of the 1970s has shaken up the global energy landscape as much as shale gas. Advances in drilling technology have made vast resources of gas and oil accessible, which until this point had been considered stranded. The Energy Information Agencys latest assessment (EIA, 2013) of worldwide recoverable resources estimates 345 billion barrels of shale oil and 7299 trillion cubic feet (1 ft 3 % 28.3 L) of shale gas resources, constituting about 10 % of the world's total recoverable oil resources and as much as 32 % of the recoverable global gas reserves.While much of the world is still struggling with the development of the necessary technology to exploit these resources (and considering the robust economic and environmental assessments that inform policies to guide this new industry), the United States (US), which has the worlds second largest shale oil reserves and fourth largest shale gas reserves according to the EIA, has taken a global lead by engaging in a rapid expansion of this industry. This expansion has caused a dramatic drop in cost of US natural gas for end consumers and industrial users alike, and has given the US industry a cost advantage over global competitors (due to the much lower degree of global integration of the gas market as compared to the world oil market) with ripple effects across the US economy, such as a current resurgence of the domestic chemical industry, which had experienced a decades-long exodus from the US. This is a staggering change in development which has put the US on a path upon which it is expected to cut its dependence on foreign oil in half and become a net exporter of natural gas before the end of this decade.The sudden, transformative impact of two converging developments-concurrent improvements in hydraulic fracking and horizontal drilling technology-can serve as a textbook example of how long-term, incremental technological development can lead to dramatic, discontinuous change, once it is adopted. It is often argued that there is no technological "silver bullet" to our energy problems, and the shale gas development certainly does not invalidate this statement. However, it does highlight that "historic" projections of our energy future that do not-or insufficiently-account for slow or hidden developments are likely to result not only in inaccurate, but fundamentally flawed projections (with equal potential for over-and underestimations). This leaves both industry and policy makers in a conundrum, as long-term decisions must be made within a framework marred with large uncertainties.It is still unclear how the cheap supply of natural gas will affect the long-term development of the US industry and the global energy landscape. Predictions vary from a short lived "shot-in-the-arm" with little or no long-term benefit, to a strong and lasting resurgence of American manufacturing. The latter will depend strongly on whether shale gas resources will start to be exploited in other parts of the world as well, which would undermine the cu...

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“…The imidoyl chloride 347a is transformed into a bis-silylated difluoroenamine 353 on treating 347a with metal magnesium in THF at 0 8C [131]. The Mg-promoted defluorination of the initially formed imidoyl silane 351 takes place under the conditions in a similar manner as the defluorination of trifluoromethylimines [132]. Both the N-Si and C-Si bonds involved in 353 are activated under either Lewis acid-or KF-catalyzed conditions.…”

Section: Trifluoroacetimidoyl Silanesmentioning

confidence: 99%

First synthesis of 3,3-difluoroserine and cysteine derivatives via Mg(0)-promoted selective CF bond cleavage of trifluoromethylimines

Cited by 76 publications

References 23 publications

Fluorinated amino acids: compatibility with native protein structures and effects on protein–protein interactions

Fluorinated amino acids: compatibility with native protein structures and effects on protein–protein interactions

Shale Gas Technology: A Special Issue

Functionalized fluoroalkyl and alkenyl silanes: Preparations, reactions, and synthetic applications

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