Expanding the scope of the Newman–Kwart rearrangement — A computational assessment

Heiko Jacobsen; James P Donahue

doi:10.1139/v06-161

Expanding the scope of the Newman–Kwart rearrangement — A computational assessment

Canadian Journal of Chemistry ◽

10.1139/v06-161 ◽

2006 ◽

Vol 84 (11) ◽

pp. 1567-1574 ◽

Cited By ~ 18

Author(s):

Heiko Jacobsen ◽

James P Donahue

Keyword(s):

Transition State ◽

Ab Initio ◽

Density Functional Calculations ◽

Density Functional ◽

Structural Element ◽

Cyclic Transition ◽

Cyclic Transition State ◽

Localized Orbital

The Newman–Kwart rearrangement (NKR) has been studied for a variety of thioncarbamates using density functional (B3LYP) and ab initio (MP2) methodologies. The results confirm and support the generally accepted mechanism that the NKR proceeds through a four-membered cyclic transition state. The presence of a π system connected via an oxygen linkage to a thiocarbonyl functionality is identified as a crucial structural element for the NKR. The calculations further suggest that the NKR might also be feasible for thioncarbamates derived from π system containing groups other than phenols such as ethenol, ethenediol, and butadienol. The NKR is compared with the Schönberg rearrangements of thioncarbonates.Key words: density functional calculations, localized orbital locator, oxygen–sulfur transposition, thiols.

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Ab Initio Density Functional Calculations of Deuterium Kinetic Isotope Effects for Decomposition of Dimethylnitramine

The Journal of Physical Chemistry A ◽

10.1021/jp962326t ◽

1997 ◽

Vol 101 (7) ◽

pp. 1370-1373 ◽

Cited By ~ 11

Author(s):

Nathan J. Harris ◽

Koop Lammertsma

Keyword(s):

Ab Initio ◽

Density Functional Calculations ◽

Density Functional ◽

Isotope Effects ◽

Kinetic Isotope Effects ◽

Kinetic Isotope

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The conversion of 3- and 4-hydroxybenzonitriles (m- and p-cyanophenols) into oxyanions, followed by IR spectra, ab initio and density functional calculations

Journal of Molecular Structure ◽

10.1016/j.molstruc.2003.12.022 ◽

2004 ◽

Vol 692 (1-3) ◽

pp. 23-35 ◽

Cited By ~ 12

Author(s):

Miglena K. Georgieva ◽

Polina N. Angelova ◽

Ivan G. Binev

Keyword(s):

Ir Spectra ◽

Ab Initio ◽

Density Functional Calculations ◽

Density Functional

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ChemInform Abstract: REMOTE PHOTOCYCLIZATION OF (DIBENZYLAMINO)ETHYL BENZOYLACETATE. INTRAMOLECULAR HYDROGEN ABSTRACTION THROUGH A TEN-MEMBERED CYCLIC TRANSITION STATE

Chemischer Informationsdienst ◽

10.1002/chin.198527261 ◽

1985 ◽

Vol 16 (27) ◽

Author(s):

T. HASEGAWA ◽

K. MIYATA ◽

T. OGAWA ◽

N. YOSHIHARA ◽

M. YOSHIOKA

Keyword(s):

Transition State ◽

Hydrogen Abstraction ◽

Cyclic Transition ◽

Cyclic Transition State ◽

Intramolecular Hydrogen

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A Bifunctional B,N‐Based Asymmetric Catalytic Nitrostyrene‐ Michael Addition Acting through a 10‐Membered Ring Cyclic Transition State

Helvetica Chimica Acta ◽

10.1002/hlca.202100199 ◽

2021 ◽

Author(s):

Yihao Du ◽

Ozlem Sari ◽

Safiye S. Erdem ◽

Andrew Whiting

Keyword(s):

Transition State ◽

Michael Addition ◽

Membered Ring ◽

Cyclic Transition ◽

Asymmetric Catalytic ◽

Cyclic Transition State

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Atomic configurations of Pd atoms in PdAu(111) and PdAu(100) surface alloys: Ab initio density functional calculations

Chemical Physics Letters ◽

10.1016/j.cplett.2008.11.077 ◽

2009 ◽

Vol 468 (4-6) ◽

pp. 162-165 ◽

Cited By ~ 20

Author(s):

H.J. Gotsis ◽

I. Rivalta ◽

E. Sicilia ◽

N. Russo

Keyword(s):

Ab Initio ◽

Density Functional Calculations ◽

Density Functional ◽

Surface Alloys

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Divergent Reactivity of Stannane and Silane in the Trifluoromethylation of PdII: Cyclic Transition State versus Difluorocarbene Release

Angewandte Chemie ◽

10.1002/ange.201808229 ◽

2018 ◽

Vol 130 (46) ◽

pp. 15301-15305 ◽

Cited By ~ 2

Author(s):

Maoping Pu ◽

Italo A. Sanhueza ◽

Erdem Senol ◽

Franziska Schoenebeck

Keyword(s):

Transition State ◽

Cyclic Transition ◽

Cyclic Transition State

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Molecular photochemistry. XXXVI. Photochemistry of some .alpha.-oxopropiophenones. Evidence for an unusual cyclic transition state for hydrogen abstraction

Journal of the American Chemical Society ◽

10.1021/ja00728a040 ◽

1970 ◽

Vol 92 (25) ◽

pp. 7467-7470 ◽

Cited By ~ 14

Author(s):

Nicholas J. Turro ◽

Ta-Jyh. Lee

Keyword(s):

Transition State ◽

Hydrogen Abstraction ◽

Cyclic Transition ◽

Cyclic Transition State

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Mass Spectrometry in Structural and Stereochemical Problems. LXXXV.1The Nature of the Cyclic Transition State in Hydrogen Rearrangements of Aliphatic Amines2,3

Journal of the American Chemical Society ◽

10.1021/ja00952a040 ◽

1965 ◽

Vol 87 (24) ◽

pp. 5752-5756 ◽

Cited By ~ 51

Author(s):

Carl Djerassi ◽

Catherine Fenselau

Keyword(s):

Mass Spectrometry ◽

Transition State ◽

Cyclic Transition ◽

Cyclic Transition State

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Bonding at metal-ceramic interfaces; AB Initio density-functional calculations for Ti and Ag on MgO

Acta Metallurgica et Materialia ◽

10.1016/0956-7151(92)90257-f ◽

1992 ◽

Vol 40 ◽

pp. S1-S10 ◽

Cited By ~ 156

Author(s):

U. Scho¨nberger ◽

O.K. Andersen ◽

M. Methfessel

Keyword(s):

Ab Initio ◽

Density Functional Calculations ◽

Density Functional ◽

Metal Ceramic ◽

Ceramic Interfaces

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THEORETICAL STUDY OF HYDROGEN BONDED CLUSTERS OF AMMONIA AND FULMINIC ACID

Journal of Theoretical and Computational Chemistry ◽

10.1142/s021963360800368x ◽

2008 ◽

Vol 07 (02) ◽

pp. 277-286 ◽

Cited By ~ 2

Author(s):

ABEDIEN ZABARDASTI ◽

SAEID AMANI ◽

MARYAM SALEHNASSAJ ◽

ALI H. KIANFARD

Keyword(s):

Ab Initio ◽

Density Functional Calculations ◽

Cluster Size ◽

Density Functional ◽

Theoretical Study ◽

Cooperative Effect ◽

Stabilization Energy ◽

Topological Parameters ◽

Hydrogen Bonded

Ab initio and density functional calculations are used to analyze the interaction between a molecule of fulminic acid with one, two, three, and four molecules of ammonia along with a 2:2 complex at B3LYP/6-311++G(d, p) and MP2/6-311++G(d, p) computational levels. Cooperative effect (CE) in terms of stabilization energy of clusters is calculated and discussed as well. For the studied clusters, the CE is increased with increasing cluster size. Red shifts of H – C stretching frequency for complexes involving HCNO as H -donor are predicted. Atom in molecules is used to analyze the cooperative effect on topological parameters.

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