Cis -1,2-Aminohydroxylation of Alkenes Involving a Catalytic Cycle of Osmium(III) and Osmium(V) Centers

OsV(O)(NHTs) Active Oxidant with a Macrocyclic Tetradentate Ligand

Hideki Sugimoto, Akine Mikami, Kenichiro Kai, P. K. Sajith, Yoshihito Shiota, Kazunari Yoshizawa, Kaori Asano, Takeyuki Suzuki, Shinobu Itoh

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

Catalytic activity of [OsIII(OH)(H2O)(L-N4Me2)](PF6)2 (1: L-N4Me2 = N,N′-dimethyl-2,11-diaza-[3,3](2,6)pyridinophane) in 1,2-cis-aminohydroxylation of alkenes with sodium N-chloro-4-methylbenzenesulfonamide (chloramine-T) is explored. Simple alkenes as well as those containing several types of substituents are converted to the corresponding 1,2-aminoalcohols in modest to high yields. The aminoalcohol products have exclusively cis conformation with respect to the introduced -OH and -NHTs groups. The spectroscopic measurements including cold mass spectroscopic study of the reaction product of complex 1 and chloromine-T as well as density functional theory (DFT) calculations indicate that an oxido-aminato-osmium(V) species [OsV(O)(NHTs)(L-N4Me2)](PF6)2 (2) is an active oxidant for the aminohydroxylation. The DFT calculations further indicate that the reaction involves a [3 + 2] cycloaddition between 2 and alkene, and the regioselectivity in the aminohydroxylation of unsymmetrical alkenes is determined by the orientation that bears less steric hindrance from the tosylamino group, which leads to the energetically more preferred product isomer.

Original languageEnglish
Pages (from-to)7073-7082
Number of pages10
JournalInorganic Chemistry
Volume54
Issue number14
DOIs
Publication statusPublished - Jul 20 2015

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Osmium
osmium
Alkenes
Oxidants
alkenes
Ligands
ligands
cycles
Density functional theory
density functional theory
Regioselectivity
Cycloaddition
cycloaddition
products
bears
Reaction products
Isomers
reaction products
Conformations
catalytic activity

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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Cis -1,2-Aminohydroxylation of Alkenes Involving a Catalytic Cycle of Osmium(III) and Osmium(V) Centers : OsV(O)(NHTs) Active Oxidant with a Macrocyclic Tetradentate Ligand. / Sugimoto, Hideki; Mikami, Akine; Kai, Kenichiro; Sajith, P. K.; Shiota, Yoshihito; Yoshizawa, Kazunari; Asano, Kaori; Suzuki, Takeyuki; Itoh, Shinobu.

In: Inorganic Chemistry, Vol. 54, No. 14, 20.07.2015, p. 7073-7082.

Research output: Contribution to journalArticle

Sugimoto, Hideki ; Mikami, Akine ; Kai, Kenichiro ; Sajith, P. K. ; Shiota, Yoshihito ; Yoshizawa, Kazunari ; Asano, Kaori ; Suzuki, Takeyuki ; Itoh, Shinobu. / Cis -1,2-Aminohydroxylation of Alkenes Involving a Catalytic Cycle of Osmium(III) and Osmium(V) Centers : OsV(O)(NHTs) Active Oxidant with a Macrocyclic Tetradentate Ligand. In: Inorganic Chemistry. 2015 ; Vol. 54, No. 14. pp. 7073-7082.
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abstract = "Catalytic activity of [OsIII(OH)(H2O)(L-N4Me2)](PF6)2 (1: L-N4Me2 = N,N′-dimethyl-2,11-diaza-[3,3](2,6)pyridinophane) in 1,2-cis-aminohydroxylation of alkenes with sodium N-chloro-4-methylbenzenesulfonamide (chloramine-T) is explored. Simple alkenes as well as those containing several types of substituents are converted to the corresponding 1,2-aminoalcohols in modest to high yields. The aminoalcohol products have exclusively cis conformation with respect to the introduced -OH and -NHTs groups. The spectroscopic measurements including cold mass spectroscopic study of the reaction product of complex 1 and chloromine-T as well as density functional theory (DFT) calculations indicate that an oxido-aminato-osmium(V) species [OsV(O)(NHTs)(L-N4Me2)](PF6)2 (2) is an active oxidant for the aminohydroxylation. The DFT calculations further indicate that the reaction involves a [3 + 2] cycloaddition between 2 and alkene, and the regioselectivity in the aminohydroxylation of unsymmetrical alkenes is determined by the orientation that bears less steric hindrance from the tosylamino group, which leads to the energetically more preferred product isomer.",
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T2 - OsV(O)(NHTs) Active Oxidant with a Macrocyclic Tetradentate Ligand

AU - Sugimoto, Hideki

AU - Mikami, Akine

AU - Kai, Kenichiro

AU - Sajith, P. K.

AU - Shiota, Yoshihito

AU - Yoshizawa, Kazunari

AU - Asano, Kaori

AU - Suzuki, Takeyuki

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AB - Catalytic activity of [OsIII(OH)(H2O)(L-N4Me2)](PF6)2 (1: L-N4Me2 = N,N′-dimethyl-2,11-diaza-[3,3](2,6)pyridinophane) in 1,2-cis-aminohydroxylation of alkenes with sodium N-chloro-4-methylbenzenesulfonamide (chloramine-T) is explored. Simple alkenes as well as those containing several types of substituents are converted to the corresponding 1,2-aminoalcohols in modest to high yields. The aminoalcohol products have exclusively cis conformation with respect to the introduced -OH and -NHTs groups. The spectroscopic measurements including cold mass spectroscopic study of the reaction product of complex 1 and chloromine-T as well as density functional theory (DFT) calculations indicate that an oxido-aminato-osmium(V) species [OsV(O)(NHTs)(L-N4Me2)](PF6)2 (2) is an active oxidant for the aminohydroxylation. The DFT calculations further indicate that the reaction involves a [3 + 2] cycloaddition between 2 and alkene, and the regioselectivity in the aminohydroxylation of unsymmetrical alkenes is determined by the orientation that bears less steric hindrance from the tosylamino group, which leads to the energetically more preferred product isomer.

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