A practical protocol for the α-amination of ketones (up to 99% yield) has been developed via the Mukaiyama aldol reaction of in situ generated nitrosocarbonyl compounds. The reaction with silyl enol ethers having a disilane (-SiMe2TMS) backbone proceeded not only with perfect N-selectivity but concomitant N-O bond cleavage was also accomplished. Such a cascade of C-N bond formation and N-O bond cleavage in a single step was heretofore unknown in the field of nitrosocarbonyl chemistry. A very high diastereoselectivity (dr = 19 : 1) was accomplished using (-)-menthol derived chiral nitrosocarbonyl compounds. © The Royal Society of Chemistry 2015.

Mahiuddin Baidya

Department Of Chemistry

Isai Ramakrishna

Gowri Sankar Grandhi

AMINOKETONE

carbon

carbonyl derivative

ether derivative

MENTHOL

nitrogen

nitroso derivative

NITROSOCARBONYL DERIVATIVE

Oxygen

silane derivative

SILYL ENOL ETHER

solvent

unclassified drug

acetonitrile

acetonitrile derivative

Copper

Cupric chloride

ketone

pyridine derivative

amination

article

chemical bond

chemical reaction

chirality

controlled study

covalent bond

diastereoisomer

MUKAIYAMA REACTION

one pot synthesis

reaction time

Silylation

stereochemistry

chemistry

Acetonitriles

Ketones

Nitroso compounds

Pyridines

IIT Madras is a public technical and research university located in Chennai, Tamil Nadu. Founded in 1959, it is recognised as an Institute of National Importance.

IIT Madras has been ranked as the top engineering institute in India for four years in a row by the National Institutional Ranking Framework of the MHRD

It currently offers undergraduate, postgraduate and research degrees across 16 disciplines in Engineering, Sciences, Humanities and Management. About 596 faculty belonging to science and engineering departments and centres of the Institute are engaged in teaching, research and industrial consultancy.

IIT Madras

Chemical Communications

Functionalization of carbonyls, particularly with a heteroatom subunit, is an important synthetic transformation. Utilization of ambident electrophiles for such a strategy is advantageous because two different heteroatom units can be installed from a single source under judicial reaction conditions. Recently, there have been increased examples for the construction of C–O and C–N bonds using nitroso compounds, a prototype of ambident electrophiles. In this short review, we discuss the advantages and challenges of exploiting nitroso compounds in organic synthesis with specific focus on nitroso aldol type processes for the direct hydroxylation and amination of carbonyl compounds. 1 Introduction 2 Prime Challenges in Nitroso Aldol Reactions 3 Direct Hydroxylation Reactions 4 Direct Amination Reactions 5 Conclusion and Outlook Copyright © 2017, Georg Thieme Verlag. All rights reserved.

Synthesis (Germany)

Ambident Reactivity of Nitroso Compounds for Direct Amination and Hydroxylation of Carbonyls

Functionalization of carbonyls, particularly with a heteroatom subunit, is an important synthetic transformation. Utilization of ambident electrophiles for such a strategy is advantageous because two different heteroatom units can be installed from a single source under judicial reaction conditions. Recently, there have been increased examples for the construction of C-O and C-N bonds using nitroso compounds, a prototype of ambident electrophiles. In this short review, we discuss the advantages and challenges of exploiting nitroso compounds in organic synthesis with specific focus on nitroso aldol type processes for the direct hydroxylation and amination of carbonyl compounds. 1 Introduction 2 Prime Challenges in Nitroso Aldol Reactions 3 Direct Hydroxylation Reactions 4 Direct Amination Reactions 5 Conclusion and Outlook. © 2017 Georg Thieme Verlag Stuttgart. New York-Synthesis.

A Brønsted acid mediated N-O bond cleavage for α-amination of ketones has been developed through the nitroso aldol reaction of less-reactive aromatic nitroso compounds and silyl enol ethers having a disilane (-SiMe2TMS) backbone. This transformation is operationally simple and scalable, offering structurally diverse α-amino ketones in high yields (up to 98%) with complete regioselectivity. It represents a mechanistically unique and rare example of a metal-free N-O bond cleavage process. © The Royal Society of Chemistry 2016.

Fulltext

Brønsted acid mediated N-O bond cleavage for α-amination of ketones through the aromatic nitroso aldol reaction

Organic Letters

Fe-Catalyzed Direct α C–H Amination of Carbonyl Compounds

Synlett

Asymmetric Synthesis of Tertiary α-Hydroxy Phosphonic Acid Derivatives under Aerobic Oxidation Conditions

Angewandte Chemie International Edition

The Electrophilic α-Amination of α-Alkyl-β-Ketoesters with In Situ Generated Nitrosoformates

Copper-Catalyzed Amination of Ketene Silyl Acetals with Hydroxylamines: Electrophilic Amination Approach to α-Amino Acids

Journal of the American Chemical Society

Catalytic Enantioselective O-Nitrosocarbonyl Aldol Reaction of β-Dicarbonyl Compounds

The Mukaiyama aldol reaction of in situ generated nitrosocarbonyl compounds: Selective C-N bond formation and N-O bond cleavage in one-pot for α-amination of ketones

Journal	Data powered by TypesetChemical Communications
Publisher	Data powered by TypesetRoyal Society of Chemistry
ISSN	13597345
Open Access	No