Nickel-Catalyzed Coupling Reactions of Alkyl Electrophiles, Including Unactivated Tertiary Halides, To Generate Carbon–Boron Bonds

Through the use of a catalyst formed in situ from NiBr2·diglyme and a pybox ligand (both of which are commercially available), we have achieved our first examples of coupling reactions of unactivated tertiary alkyl electrophiles, as well as our first success with nickel-catalyzed couplings that generate bonds other than C–C bonds. Specifically, we have determined that this catalyst accomplishes Miyaura-type borylations of unactivated tertiary, secondary, and primary alkyl halides with diboron reagents to furnish alkylboronates, a family of compounds with substantial (and expanding) utility, under mild conditions; indeed, the umpolung borylation of a tertiary alkyl bromide can be achieved at a temperature as low as −10 °C. The method exhibits good functional-group compatibility and is regiospecific, both of which can be issues with traditional approaches to the synthesis of alkylboronates. In contrast to seemingly related nickel-catalyzed C–C bond-forming processes, tertiary halides are more reactive than secondary or primary halides in this nickel-catalyzed C–B bond-forming reaction; this divergence is particularly noteworthy in view of the likelihood that both transformations follow an inner-sphere electron-transfer pathway for oxidative addition

Nickel-Catalyzed Enantioconvergent Borylation of Racemic Secondary Benzylic Electrophiles

Nickel‐catalyzed cross‐coupling has emerged as the most versatile approach to date for achieving enantioconvergent carbon–carbon bond formation using racemic alkyl halides as electrophiles. In contrast, there have not yet been reports of the application of chiral nickel catalysts to the corresponding reactions with heteroatom nucleophiles to produce carbon–heteroatom bonds with good enantioselectivity. Herein, we establish that a chiral nickel/pybox catalyst can borylate racemic secondary benzylic chlorides to provide enantioenriched benzylic boronic esters, a highly useful family of compounds in organic synthesis. The method displays good functional group compatibility (e.g., being unimpeded by the presence of an indole, a ketone, a tertiary amine, or an unactivated alkyl bromide), and both of the catalyst components (NiCl_2⋅glyme and the pybox ligand) are commercially available

Nickel-Catalyzed Enantioconvergent Borylation of Racemic Secondary Benzylic Electrophiles

Nickel‐catalyzed cross‐coupling has emerged as the most versatile approach to date for achieving enantioconvergent carbon–carbon bond formation using racemic alkyl halides as electrophiles. In contrast, there have not yet been reports of the application of chiral nickel catalysts to the corresponding reactions with heteroatom nucleophiles to produce carbon–heteroatom bonds with good enantioselectivity. Herein, we establish that a chiral nickel/pybox catalyst can borylate racemic secondary benzylic chlorides to provide enantioenriched benzylic boronic esters, a highly useful family of compounds in organic synthesis. The method displays good functional group compatibility (e.g., being unimpeded by the presence of an indole, a ketone, a tertiary amine, or an unactivated alkyl bromide), and both of the catalyst components (NiCl_2⋅glyme and the pybox ligand) are commercially available

Controlled Synchronization of One Class of Nonlinear Systems under Information Constraints

Output feedback controlled synchronization problems for a class of nonlinear unstable systems under information constraints imposed by limited capacity of the communication channel are analyzed. A binary time-varying coder-decoder scheme is described and a theoretical analysis for multi-dimensional master-slave systems represented in Lurie form (linear part plus nonlinearity depending only on measurable outputs) is provided. An output feedback control law is proposed based on the Passification Theorem. It is shown that the synchronization error exponentially tends to zero for sufficiantly high transmission rate (channel capacity). The results obtained for synchronization problem can be extended to tracking problems in a straightforward manner, if the reference signal is described by an {external} ({exogenious}) state space model. The results are applied to controlled synchronization of two chaotic Chua systems via a communication channel with limited capacity.Comment: 8 pages, 2 figure

Modern microwave methods in solid state inorganic materials chemistry: from fundamentals to manufacturing

No abstract available

Nickel-Catalyzed Coupling Reactions of Alkyl Electrophiles, Including Unactivated Tertiary Halides, To Generate Carbon–Boron Bonds

Through the use of a catalyst formed in situ from NiBr[subscript 2]·diglyme and a pybox ligand (both of which are commercially available), we have achieved our first examples of coupling reactions of unactivated tertiary alkyl electrophiles, as well as our first success with nickel-catalyzed couplings that generate bonds other than C–C bonds. Specifically, we have determined that this catalyst accomplishes Miyaura-type borylations of unactivated tertiary, secondary, and primary alkyl halides with diboron reagents to furnish alkylboronates, a family of compounds with substantial (and expanding) utility, under mild conditions; indeed, the umpolung borylation of a tertiary alkyl bromide can be achieved at a temperature as low as −10 °C. The method exhibits good functional-group compatibility and is regiospecific, both of which can be issues with traditional approaches to the synthesis of alkylboronates. In contrast to seemingly related nickel-catalyzed C–C bond-forming processes, tertiary halides are more reactive than secondary or primary halides in this nickel-catalyzed C–B bond-forming reaction; this divergence is particularly noteworthy in view of the likelihood that both transformations follow an inner-sphere electron-transfer pathway for oxidative addition.National Institute of General Medical Sciences (U.S.) (Grant R01-GM62871

Nickel-Catalyzed Coupling Reactions of Alkyl Electrophiles, Including Unactivated Tertiary Halides, To Generate Carbon–Boron Bonds

Through the use of a catalyst formed in situ from NiBr₂·diglyme and a pybox ligand (both of which are commercially available), we have achieved our first examples of coupling reactions of unactivated tertiary alkyl electrophiles, as well as our first success with nickel-catalyzed couplings that generate bonds other than C–C bonds. Specifically, we have determined that this catalyst accomplishes Miyaura-type borylations of unactivated tertiary, secondary, and primary alkyl halides with diboron reagents to furnish alkylboronates, a family of compounds with substantial (and expanding) utility, under mild conditions; indeed, the umpolung borylation of a tertiary alkyl bromide can be achieved at a temperature as low as −10 °C. The method exhibits good functional-group compatibility and is regiospecific, both of which can be issues with traditional approaches to the synthesis of alkylboronates. In contrast to seemingly related nickel-catalyzed C–C bond-forming processes, tertiary halides are <i>more</i> reactive than secondary or primary halides in this nickel-catalyzed C–B bond-forming reaction; this divergence is particularly noteworthy in view of the likelihood that both transformations follow an inner-sphere electron-transfer pathway for oxidative addition

Obtaining of hydroxylated fullerenes Y@C82OX(OH)Y, Y2@C82OX(OH)Y, Y2C2@C82OX(OH)Y and electrophysical characteristic of composite film based thereon

The article presents, for the first time, the results of the research on composite film obtained from hydroxylated endohedral metallofullerenes (EMF) Y@C82, Y2@C82, with Y2C2@C82 and highest fullerenes as dopant. The composite film has been established to have electric conductivity and to be a ferroelectric with the value of residual polarization of ~0.75 mkC/cm2. The impedance spectroscopy of this sample allowed us to determine dispersion of dielectric permittivity and conductivity in the range of frequencies of 0.5Hz–100MHz. It is stated that the value of the high-frequency dielectric permittivity of films is e' = 2.8. However, with reduction in the electric field frequency, real and imaginary parts of e increase to values ~10^4–10^5. Such increase in dielectric permittivity is connected with increase in polarizing caused by accumulation of mobile electric charges (electrons of ions, protons) on boundaries of the structural defects of a film, which are divided by thin dielectric interlayers. The film is solid electrolyte with the ionic conductivity of ~5*10^(-7) S/cm