Volume 44 Number 27 21 July 2015 Pages 12013–12434 Dalton Transactions An international journal of inorganic chemistry www.rsc.org/dalton ISSN 1477-9226 PERSPECTIVE Jérôme Hannedouche et al. Recent developments in alkene hydro-functionalisation promoted by homogeneous catalysts based on earth abundant elements: formation of C–N, C–O and C–P bond Dalton Transactions View Article Online PERSPECTIVE View Journal | View Issue Recent developments in alkene hydro- functionalisation promoted by homogeneous Cite this: Dalton Trans., 2015, 44, 12029 catalysts based on earth abundant elements: formation of C–N, C–O and C–P bond Violeta Rodriguez-Ruiz,a Romain Carlino,a Sophie Bezzenine-Lafollée,a Richard Gil,a Damien Prim,b Emmanuelle Schulza,c and Jérôme Hannedouche*a,c This Perspective article provides an overview of the recent advancements in the field of intra- and inter- molecular C–N, C–O and C–P bond formation by hydroamination, hydroalkoxylation, hydrophosphina- Received 20th January 2015, tion, hydrophosphonylation or hydrophosphinylation of unactivated alkenes, including allenes, 1,3-dienes Accepted 16th March 2015 and strained alkenes, promoted by (chiral) homogeneous catalysts based on earth abundant elements of DOI: 10.1039/c5dt00280j the s and p blocks, the first row transition metals and the rare-earth metals. The relevant literature from Creative Commons Attribution-NonCommercial 3.0 Unported Licence. www.rsc.org/dalton 2009 until late 2014 has been covered. 1. Introduction maceuticals, fine and bulk chemicals, agrochemicals, biologi- cal and coordination chemistry or catalysis amongst others The wide applications of nitrogen-, oxygen- and phosphorus- have driven the interest of the scientific community with a based organic compounds in various domains such as phar- strong demand for the development of sustainable, more selec- tive and efficient processes for their syntheses. Among the plethora of synthesis routes, the addition of E–H (E = N, O, P) a This article is licensed under a Univ Paris-Sud, ICMMO, UMR 8182, Orsay, F-91405, France. across an unactivated carbon–carbon double bond, the more E-mail: [email protected] generally called hydrofunctionalisation (or hydroelementa- bUniversité Versailles Saint-Quentin, ILV, UMR8180, 45, avenue des Etats-Unis, 1 Versailles, F-78035, France tion) reaction of unactivated alkene, promoted by a metal or cCNRS, Orsay, F-91405, France metal-free catalyst is a very promising field of research towards Open Access Article. Published on 16 March 2015. Downloaded 10/3/2021 12:54:49 PM. Violeta Rodriguez-Ruiz received Romain Carlino was born in her B.Sc. in Pharmacy at the Uni- 1988 in Monaco. He obtained versity of Valencia, Spain. She his diploma from Ecole Natio- got her M.Sc. in Chemistry at the nale Supérieure de Chimie de Technical Institute of Chemistry Clermont-Ferrand and his (ITQ, UPV-CSIC), where she master degree at Université carried out her Ph.D. at Prof. Blaise Pascal in 2013. He is cur- Corma’s group. In 2011, she rently a PhD student at ICMMO obtained a Marie Curie-ITN (Université Paris-Sud) working Experienced Researcher fellow- on rare-earth complexes for cata- ship to work at the “Institut lytic applications in hydroalko- Galien Paris-Sud” (Faculty of xylation reaction under the Violeta Rodriguez-Ruiz Pharmacy, CNRS-Université Romain Carlino supervision of Dr Sophie Bezze- Paris-Sud). In 2012, she joined nine-Lafollée and Dr Richard the “Laboratory of Molecular Catalysis” (ICMMO, Faculty of Gil. Sciences, CNRS-Université Paris-Sud) as a Post-Doctoral Fellow. Since 2014, she works at the “Laboratory for Vascular Trans- lational Science” (Institut Galilée, Université Paris13-INSERM) as Temporary Lecturer and Research Assistant. This journal is © The Royal Society of Chemistry 2015 Dalton Trans.,2015,44, 12029–12059 | 12029 View Article Online Perspective Dalton Transactions the development of an economic and environmentally friendly This Perspective article will outline some of the recent synthetic methodology. Indeed, the hydrofunctionalisation advancements in the field of intra- and inter-molecular C–N, reaction provides a 100% atom efficiency and waste-free C–O and C–P bond formation by hydroamination, hydroalkoxy- process from relatively low-cost and ubiquitous starting lation, hydrophosphination, hydro-phosphonylation or hydro- materials. Furthermore, catalysis brings the opportunity to phosphinylation of unactivated alkenes, including allenes, 1,3- fine-tune the regio-, chemo- and stereoselectivity of the overall dienes and strained alkenes, promoted by (chiral) catalytic transformation by a perfect synergy between the metal and the systems based on earth abundant elements. The hydration of ligand(s) or by the direct design of a metal-free system. alkenes is not included and the reader should refer to reported However, despite the inherent interesting features of the trans- reviews on the topic.7 This article will focus on systems based formation, it is very challenging to control the regioselectivity on Group 1–3 elements, the most relevant first-row transition of this reaction providing exclusively the Markovnikov or the metal elements of the field (titanium, iron, cobalt, nickel, anti-Markovnikov adduct. As a general trend, Markovnikov copper and zinc) and also the block p element aluminum. It is selectivity is the most common selectivity noticed in the beyond the scope of this article to comprehensively review all addition reactions of N–H and O–H onto unactivated alkenes the research activity of this broad field and literature coverage while the addition of P–H provides usually the anti-Markovni- has been mainly limited from 2009 until 2014, even if a few kov product. For the corresponding addition reaction, few con- representative reports appeared earlier are included. This – tributions exhibit the opposite regioselectivity.2 4 These article has been divided according to the Group, the element features highlight the challenges to access both regioisomeric within the Group and the type of C–E (E = N, O, P) bond products which are all of synthetic value. Additionally to the formed in the transformation. For a broader overview, the regioselectivity, the control of stereoselectivity of the newly latest developments in metal free-catalysed C–E (E = N, O, P) generated stereogenic carbon of the branched product is also bond formation by alkene hydrofunctionalisation have also an important issue of this process. For example, the intermole- been included and will start this Perspective. Creative Commons Attribution-NonCommercial 3.0 Unported Licence. cular and highly enantio- and regioselective addition of amines to simple aliphatic alkenes still remains one of the most unresolved problems in alkene hydroamination5 as is the 2. Metal-free catalysts control of the enantioselectivity in alkene hydroalkoxyla- – – tion.3d e,6 The last decades have witnessed an intensive 2.1 C N bond formation research activity focusing on the development of metal-based 2.1.1 Brønsted acid catalysts. Over the years, alkene hydro- and metal-free catalysts to promote the addition of E–H across amination promoted by Brønsted acid catalysts has naturally an unactivated carbon–carbon double bond intra- and inter- attracted the attention of the scientific community as an eco- molecularly. Although tremendous progresses have been friendly methodology for metal-free C–N bond formation. This article is licensed under a gained from the study of precious metal catalysts,1 the growing Although significant developments have been gained in broad- request for novel, more economical and eco-friendly catalytic ening the scope of the racemic transformation,8 the most systems has stimulated the exploration of earth abundant recent achievements have been on the challenging control of Open Access Article. Published on 16 March 2015. Downloaded 10/3/2021 12:54:49 PM. elements as alternatives to address some of the issues. the stereoselectivity of the N–H addition on the unactivated Sophie Bezzenine-Lafollée Richard Gil studied chemistry at received her Ph.D. degree from Université Paris-Sud (Orsay, Université Paris VI in 1998. After France) where he received his a postdoctoral stay on asym- PhD in 1993. His thesis work metric synthesis with Pr. P. was under the supervision of Pro- Müller at the University of fessor Jean-Claude Fiaud and Geneva, Switzerland, she spent dealt with enantioselective palla- two years in the laboratory of dium-catalysed reactions. He Pr. J. Ardisson at the University then spent one post-doctoral year of Cergy-Pontoise working on (1993–1994) at Imperial College total synthesis. She became London under the group of Pr. Maître de Conférence in Orsay Susan E. Gibson. In 1995, Sophie Bezzenine-Lafollée University in 2001, she firstly Richard Gil he went to Université de Cergy- worked with Drs F. Guibé and Pontoise and became Maître de J. Collin on lanthanides chemistry. Recently, she collaborated with Conférences in 1996. In 2002, he returned to ICMMO where he Pr. V. Gandon on silver-free two-component approach in gold cata- joined the Dr Jacqueline Collin group in which he has been inter- lysis and since 2010, she works with Dr R. Gil on enantioselective ested in lanthanide-catalysed reactions. His research interests catalysis with rare earths complexes. include enantioselective reactions catalysed by rare earths. 12030 | Dalton Trans.,2015,44, 12029–12059 This journal is © The Royal Society of Chemistry 2015 View Article Online Dalton Transactions Perspective alkene. Pioneer