Some Aspects of Reductive Amination in the Presence of Carbon Monoxide: Cyclopropyl Ketones as Bifunctional Electrophiles

Oleg I. Afanasyev; Alexey A. Tsygankov; Dmitry L. Usanov; Dmitry S. Perekalin; Alexandra D. Samoylova; Denis Chusov

doi:10.1055/s-0036-1588817

Synthesis, Table of Contents

Synthesis 2017; 49(12): 2640-2651
DOI: 10.1055/s-0036-1588817

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Some Aspects of Reductive Amination in the Presence of Carbon Monoxide: Cyclopropyl Ketones as Bifunctional Electrophiles

Authors

Oleg I. Afanasyev

^aNesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, Vavilova 28, Moscow 119991, Russian Federation
Alexey A. Tsygankov

^aNesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, Vavilova 28, Moscow 119991, Russian Federation

^dDmitry Mendeleev University of Chemical Technology of Russia, Miusskaya sq. 9, Moscow 125047, Russian Federation
Dmitry L. Usanov

^bCurrent address:Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, MA 02138, USA
Dmitry S. Perekalin

^aNesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, Vavilova 28, Moscow 119991, Russian Federation
Alexandra D. Samoylova

^cMoscow Chemical Lyceum, Tamozhenniy proezd 4, Moscow 111033, Russian Federation Email: chusov@ineos.ac.ru Email: denis.chusov@gmail.com
Denis Chusov*

^aNesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, Vavilova 28, Moscow 119991, Russian Federation

^cMoscow Chemical Lyceum, Tamozhenniy proezd 4, Moscow 111033, Russian Federation Email: chusov@ineos.ac.ru Email: denis.chusov@gmail.com

Abstract

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Abstract

We conducted detailed studies on CO-assisted reductive chemistry with cyclopropyl ketones as a special type of substrate. Multiple factors influencing the outcome of the reaction have been studied for both ruthenium and rhodium catalysis. An unusual rearrangement of aminomethylcyclopropanes was found. We showed that some reductive reactions, which were believed to proceed through a water–gas shift reaction pathway, can nonetheless take place even without an external or internal water source, indicating a more interesting reaction mechanism. Cyclopropylketones were employed as bifunctional electrophiles and, depending on the conditions, the reaction with an amine can lead to a number of products, including aminoketones, cyclopropyl methylamines, pyrrolidines or 1,4-diaminopentanes.

Key words

donor–acceptor cyclopropane - pyrrolidines - carbon monoxide - reductive amination - water–gas shift reaction - cyclopropyl amines rearrangement - ring opening

Full Text

References

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