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

研究成果: ジャーナルへの寄稿記事

5 引用 (Scopus)

抄録

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.

元の言語英語
ページ(範囲)7073-7082
ページ数10
ジャーナルInorganic chemistry
54
発行部数14
DOI
出版物ステータス出版済み - 7 20 2015

Fingerprint

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

これを引用

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.

:: Inorganic chemistry, 巻 54, 番号 14, 20.07.2015, p. 7073-7082.

研究成果: ジャーナルへの寄稿記事

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. :: Inorganic chemistry. 2015 ; 巻 54, 番号 14. pp. 7073-7082.
@article{9714504a92a74a719ffe9652773922ca,
title = "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",
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.",
author = "Hideki Sugimoto and Akine Mikami and Kenichiro Kai and Sajith, {P. K.} and Yoshihito Shiota and Kazunari Yoshizawa and Kaori Asano and Takeyuki Suzuki and Shinobu Itoh",
year = "2015",
month = "7",
day = "20",
doi = "10.1021/acs.inorgchem.5b01083",
language = "English",
volume = "54",
pages = "7073--7082",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "14",

}

TY - JOUR

T1 - Cis -1,2-Aminohydroxylation of Alkenes Involving a Catalytic Cycle of Osmium(III) and Osmium(V) Centers

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

AU - Itoh, Shinobu

PY - 2015/7/20

Y1 - 2015/7/20

N2 - 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.

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.

UR - http://www.scopus.com/inward/record.url?scp=84937701142&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84937701142&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.5b01083

DO - 10.1021/acs.inorgchem.5b01083

M3 - Article

C2 - 26126185

AN - SCOPUS:84937701142

VL - 54

SP - 7073

EP - 7082

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 14

ER -