Top Organomet Chem (2016) 56: 91–114
DOI: 10.1007/3418_2015_118
# Springer International Publishing Switzerland 2015
Published online: 16 June 2015
Catalytic C–H Bond Functionalization
of Cyclopropane Derivatives
Daniela Sustac Roman and Andre ´ B. Charette
Abstract The present work describes a comprehensive review of the functionalization of cyclopropyl C–H bonds via transition-metal catalysis. Compared to the
enormous number of publications related to direct sp
2 and sp
3 bond transformations
in the last two decades, the first full account of direct cyclopropyl C(sp
3 )–H bond
functionalization was only disclosed in 2011. Both intra- and intermolecular transformations are detailed in the review, including asymmetric reactions. In addition,
mechanistic aspects of various Pd-catalyzed cyclopropane functionalizations are
discussed.
Keywords C–H functionalization Á Catalysis Á Cyclopropane Á Palladium
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
2 Early Contributions from the Yu and Sanford Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
3 Intramolecular Direct Functionalization of Cyclopropanes . . . . . . . . . . . .. . . . . . . . . . . . . . .. . . . . 95
4 Intermolecular Direct Functionalization of Cyclopropanes . . . . . . . . . . . .. . . . . . . . . . . . . . .. . . . . 102
5 Enantioselective Direct Functionalization of Cyclopropanes . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . 106
6 Conclusion and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
D. Sustac Roman and A.B. Charette (*)
Centre in Green Chemistry and Catalysis, Department of Chemistry, Universite ´ de Montre ´al,
P.O. Box 6128, Montre ´al, QC, Canada H3C 3J7
e-mail: andre.charette@umontreal.ca
DOI: 10.1007/3418_2015_118
# Springer International Publishing Switzerland 2015
Published online: 16 June 2015
Catalytic C–H Bond Functionalization
of Cyclopropane Derivatives
Daniela Sustac Roman and Andre ´ B. Charette
Abstract The present work describes a comprehensive review of the functionalization of cyclopropyl C–H bonds via transition-metal catalysis. Compared to the
enormous number of publications related to direct sp
2 and sp
3 bond transformations
in the last two decades, the first full account of direct cyclopropyl C(sp
3 )–H bond
functionalization was only disclosed in 2011. Both intra- and intermolecular transformations are detailed in the review, including asymmetric reactions. In addition,
mechanistic aspects of various Pd-catalyzed cyclopropane functionalizations are
discussed.
Keywords C–H functionalization Á Catalysis Á Cyclopropane Á Palladium
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
2 Early Contributions from the Yu and Sanford Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
3 Intramolecular Direct Functionalization of Cyclopropanes . . . . . . . . . . . .. . . . . . . . . . . . . . .. . . . . 95
4 Intermolecular Direct Functionalization of Cyclopropanes . . . . . . . . . . . .. . . . . . . . . . . . . . .. . . . . 102
5 Enantioselective Direct Functionalization of Cyclopropanes . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . 106
6 Conclusion and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
D. Sustac Roman and A.B. Charette (*)
Centre in Green Chemistry and Catalysis, Department of Chemistry, Universite ´ de Montre ´al,
P.O. Box 6128, Montre ´al, QC, Canada H3C 3J7
e-mail: andre.charette@umontreal.ca