TY  - JOUR
A1  - Shainyan, Bagrat A.
A1  - Kleinpeter, Erich
T1  - Conformational flexibility of 4,4-dimethyl-3,4-dihydro-2H-1,4-thiasiline and its monoheterocyclic analogs
JF  - Russian journal of general chemistry
N2  - Conformational behavior of the first cyclic organosilicon vinylsulfide, 4,4-dimethyl-3,4-dihydro-2H-1,4-thiasiline as well as its monoheterocyclic analogs, 3,4-dihydro-2H-pyran, 3,4-dihydro-2H-thiopyran, and 1,1-dimethyl-1,2,3,4-tetrahydrosiline is studied in comparison with the carbocyclic analog, cyclohexene, using the methods of low-temperature NMR spectroscopy and theoretical calculations at the DFT and MP2 levels of theory. The barrier to the ring inversion with respect to that in cycloxene is increased in 3,4-dihydro-2H-pyran and 1,1-dimethyl-1,2,3,4-tetrahydrosiline, but, in contrast to the suggestions made in the literature, is decreased in 3,4-dihydro-2H-thiopyran. In 4,4-dimethyl-3,4-dihydro-2H-1,4-thiasiline the barrier is intermediate between those in the corresponding monoheterocycles, 1,1-dimethyl-1,2,3,4-tetrahydrosiline and 3,4-dihydro-2H-thiopyran. The observed variations are rationalized from the viewpoint of the interaction of the pi-electrons of the C=C double bond with the orbitals of heteroatoms in the ring. The structure of the transition state for the ring inversion is discussed.
KW  - 4,4-dimethyl-3,4-dihydro-2H-1,4-thiasiline
KW  - 1,1-dimethyl-1,2,3,4-tetrahydrosiline
KW  - 3,4-dihydro-2H-thiopyran
KW  - 3,4-dihydro-2H-pyran
KW  - onformational analysis
Y1  - 2014
U6  - https://doi.org/10.1134/S1070363214070135
SN  - 1070-3632
SN  - 1608-3350
VL  - 84
IS  - 7
SP  - 1325
EP  - 1329
PB  - Pleiades Publ.
CY  - New York
ER  - 
TY  - JOUR
A1  - Shainyan, Bagrat A.
A1  - Moskalik, Mikhail Yu
A1  - Astakhova, Vera V.
A1  - Schilde, Uwe
T1  - Novel design of 3,8-diazabicyclo[3.2.1]octane framework in oxidative sulfonamidation of 1,5-hexadiene
JF  - Tetrahedron
N2  - 1,5-Hexadiene reacts with trifluoromethanesulfonamide in the oxidative system (t-BuOCl+Nal) to give trans-2,5-bis(iodomethyl)-1-(trifluoromethylsulfonyl)pyrrolidine 5 and 3,8-bis(trifluoromethylsulfonyl)-3,8-diazabicyclo[3.2.1]octane 6. With arenesulfonamides ArSO2NH2 (Ar=Ph, Tol), the reaction stops at the formation of the trans and cis isomers of 2,5-bis(iodomethyl)-1-(arenesulfonyl)pyrrolidine 7 and 8 (1:1). The cis isomers of 7 and 8 do not undergo cyclization to the corresponding 3,8-disubstituted 3,8-diazabicyclo[3.2.1]octanes. The reaction with triflamide represents the first example of one-pot two-step route to 3,8-diazabicyclo[3.2.1]octane system. (C) 2014 Elsevier Ltd. All rights reserved.
KW  - Trifluoromethanesulfonamide
KW  - Arenesulfonamides
KW  - 1,5-Dienes
KW  - Cycloaddition
KW  - 3,8-Diazabicyclo[3.2.1]octane
KW  - X-ray
Y1  - 2014
U6  - https://doi.org/10.1016/j.tet.2014.04.095
SN  - 0040-4020
VL  - 70
IS  - 30
SP  - 4547
EP  - 4551
PB  - Elsevier
CY  - Oxford
ER  - 
TY  - JOUR
A1  - Shainyan, Bagrat A.
A1  - Moskalik, Mikhail Yu
A1  - Heydenreich, Matthias
A1  - Kleinpeter, Erich
T1  - Conformational equilibrium and dynamic behavior of bis-N-triflyl substituted 3,8-diazabicyclo[3.2.1]octane
JF  - Magnetic resonance in chemistry
N2  - Restricted rotation about the N-S partial double bonds in a bis-N-triflyl substituted 3,8-diazabicyclo[3.2.1]octane derivative 1 has been frozen at low temperature (Delta G* = 11.6 kcal mol(-1)), and the existence of all four rotamers about the two N-S bonds, 3-in, 8-in, 3-in, 8-out, 3-out, 8-in, and 3-out, 8-out, respectively, proved experimentally by NMR spectroscopy and theoretically by DFT and MP2 calculations. Copyright (C) 2014 John Wiley & Sons, Ltd.
KW  - NMR
KW  - H-1
KW  - C-13
KW  - F-19
KW  - Dynamic NMR
KW  - Conformational equilibrium
KW  - restricted N-S rotation
Y1  - 2014
U6  - https://doi.org/10.1002/mrc.4086
SN  - 0749-1581
SN  - 1097-458X
VL  - 52
IS  - 8
SP  - 448
EP  - 452
PB  - Wiley-Blackwell
CY  - Hoboken
ER  - 
TY  - JOUR
A1  - Moskalik, Mikhail Yu.
A1  - Astakhova, Vera V.
A1  - Schilde, Uwe
A1  - Sterkhova, Irina V.
A1  - Shainyan, Bagrat A.
T1  - Assembling of 3,6-diazabicyclo[3.1.0]hexane framework in oxidative triflamidation of substituted buta-1,3-dienes
JF  - Tetrahedron
KW  - Trifluoromethanesulfonamide
KW  - Arenesulfonamides
KW  - Cycloaddition
KW  - 1,3-Dienes
KW  - 3,6-Diazabicyclo[3.1.0]hexanes
KW  - X-ray
Y1  - 2014
U6  - https://doi.org/10.1016/j.tet.2014.09.050
SN  - 0040-4020
VL  - 70
IS  - 45
SP  - 8636
EP  - 8641
PB  - Elsevier
CY  - Oxford
ER  -