Introducing Chirality at Phosphorus Atoms: an Update on the Recent Synthetic Strategies for the Preparation of Optically Pure P
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Introducing Chirality at Phosphorus Atoms: An Update on the Recent Synthetic Strategies for the Preparation of Optically Pure P-Stereogenic Molecules Sébastien Lemouzy, Laurent Giordano, Damien Hérault, Gérard Buono To cite this version: Sébastien Lemouzy, Laurent Giordano, Damien Hérault, Gérard Buono. Introducing Chirality at Phosphorus Atoms: An Update on the Recent Synthetic Strategies for the Preparation of Optically Pure P-Stereogenic Molecules. European Journal of Organic Chemistry, Wiley-VCH Verlag, 2020, 2020 (23), pp.3351 - 3366. 10.1002/ejoc.202000406. hal-03180299 HAL Id: hal-03180299 https://hal.archives-ouvertes.fr/hal-03180299 Submitted on 24 Mar 2021 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. P-Chiral Phosphorus | Very Important Paper | Introducing Chirality at Phosphorus Atoms: An Update on the Recent Synthetic Strategies for the Preparation of Optically Pure P-Stereogenic Molecules Sébastien Lemouzy,*[a] Laurent Giordano,[a] Damien Hérault,*[a] and Gérard Buono[a] Abstract: The synthesis of phosphorus molecules presenting a introduction of the chiral center on the phosphorus atom. This chiral center on the P-atom, also known as P-stereogenic com- article summarizes the main synthetic approaches directed to- pounds, has long attracted the curiosity of the scientific com- wards the enantioselective synthesis of such chemical entities munity. Indeed, these chemical compounds feature many pecu- with a historical perspective. Thus, approaches based on the liar properties, allowing their use in various fields of applica- use of chiral auxiliaries attached to the phosphorus atom and tions, ranging from medicine to enantioselective catalysis. How- the use of chiral stoichiometric reagents will be discussed first, ever, their synthesis, and more particularly the introduction and as they were historically the first to be developed. Then, the retention of the chiral information on the phosphorus center, recent discoveries in the catalytic and enantioselective synthe- remains a very challenging task. That is why this review article sis and the direct optical resolution of P-chiral compounds will focuses on the recent advances in the enantioselective synthe- be discussed. sis of P-stereogenic molecules, with a particular focus on the 1. Introduction ment, mostly due to synthetic reasons. Indeed, unlike most nitrogen compounds, phosphorus compounds feature a config- The access to chiral phosphorus compounds has always been urationally stable chiral center on the heteroatom (Scheme 1).[8] considered as a challenge in modern organic synthesis. Indeed, phosphorus compounds can be used in a wide array of different application areas, by taking advantage of the two different sta- ble oxidation states (+III and +V) of the phosphorus center.[1] Indeed, phosphorus oxides usually display interesting biological properties, and thus they have been applied in medicine (as HIV protease inhibitor[2] or anticancer agents[3]) as well as crop protection (as herbicides[4] or virucides[5]). On the other hand, phosphorus(III) compounds can be used as efficient ligands for transition-metal catalysis,[6] as well as organo-catalysts them- selves.[7] Therefore, the design of chiral phosphorus(III) and (V) compounds is of utmost importance, especially in the field of asymmetric catalysis. Among these compounds, those possessing a chiral back- bone have attracted the most attention, and thus represent the vast majority of chiral phosphorus ligands and catalysts (Fig- ure 1). In parallel to these chiral phosphorus molecules, the ones featuring the chiral center on the phosphorus atom (also known as P-stereogenic compounds) have seen less develop- Figure 1. Selected phosphorus ligands attached to a chiral carbon backbone. [a] Dr. S. Lemouzy, Dr. L. Giordano, Dr. D. Hérault, Prof. G. Buono Aix Marseille Univ, CNRS, Centrale Marseille, iSm2, Marseille, France E-mail: [email protected] [email protected] https://ism2.univ-amu.fr/fr ORCID(s) from the author(s) for this article is/are available on the WWW under https://doi.org/10.1002/ejoc.202000406. Scheme 1. Configurational stability of phosphines vs. amines. These compounds can be used successfully as ligands or organ- Thus, the synthesis of P-stereogenic molecules is of para- ocatalysts in asymmetric catalysis, and they often outperform mount importance to increase the ligand portfolio in asymmet- their chiral backbone substituted counterparts in terms of ric catalysis. Since the pioneering work of Meisenheimer and enantioselectivity.[9] Lichtenstadt, who isolated the first enantioenriched P-stereo- Figure 2. Selected important dates in the preparation and use of P-stereogenic molecules. Sébastien was born in Toulouse, France in 1988. After undergraduate studies at the Institut Universitaire de Technologie (IUT) in Castres, France, he joined the Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM) in 2008, where he obtained a master in organic and biomolecular chemistry in 2011. In 2013, he started a Ph.D. under the supervision of Dr. D. Hérault and Prof. G. Buono, where he studied the synthesis and reactivity of enantio-enriched P-stereogenic (hydroxyalkyl) phosphine-boranes. After his defense he joined the group of Prof. N. Maulide at Universität Wien, Austria in 2017 as a postdoctoral associate where he worked on enantioselective Negishi-type couplings. Since 2018, he is a temporary research and teaching attaché (ATER) at ENSCM in the group of Dr. M. Taillefer. His research interests encompass phosphorus chemistry as well as enantioselective transition-metal catalysis. Laurent Giordano received in 2002 his Ph.D. from Aix-Marseille University (France) in organometallic catalysis realized under the guidance of Dr. Alfonso Tenaglia. In the same year, Laurent joined the team of Pr. Alfredo Ricci of the University of Bologna (Italy) and he worked on the development of new nitrogen-sulfur ligands and their application in asymmetric catalysis. He was appointed as lecturer at Ecole Centrale de Marseille in January 2005. He has established his research program in collaboration with Pr. Gérard Buono in the field of phosphorus organic chemistry, focused on optically pure Secondary Phosphine Oxides and their use in catalytic reactions. Damien Hérault gained his Ph.D. in 2004 from the University Claude Bernard Lyon 1 (France). His work on polymer-supported chiral ligands was supervised by Profs. C. Saluzzo and M. Lemaire. He pursued postdoctoral studies on enantioselective organocatalysis at Durham Univer- sity (UK) with Prof. A. Whiting (2005–2007). Then he came back to France, at the University of Montpellier 2, to work with Profs. G. Cerveau and R. J. P. Corriu on sugar-based hybrid materials (2008–2009). Finally, he joined the group of Prof. G. Buono at Ecole Centrale Marseille in 2009 as lecturer. Now, in the group of Prof A. Martinez, and his current research interests include phosphorus chemistry, chirality, hybrid material, and enantioselective catalysis. Gérard Buono is Emeritus professor at Ecole Centrale Marseille. He receiveda«DoctoratesSciences Physiques » at the University Aix-Marseille in 1977 on the dynamic stereochemistry of pentacoordinate phosphorus. He became Professor of Organic Chemistry in 1987 at the University of Aix-Marseille and in 2003 at the Ecole Centrale Marseille. He headed UMR CNRS “Synthesis Catalysis Chirality” (2000–2004) and the team “Chirosciences” (2008–2012) of the ISM2 UMR 7313. His research fields include asymmetric synthesis and catalysis, the design of chiral P-stereogenic organophosphorus compounds, and their applications in catalysis as ligands and as lipase inhibitors. He has published over 175 research papers and book chapters as well as 10 patents. He supervised or co-supervised 40 Ph.D. theses. genic compound (ethyl methyl phenylphosphine oxide, via res- can be reacted in the presence of organolithium or organomag- [10] 3 3 olution with (+)-bromocamphorsulfonic acid) in 1911, the nesium reagents (via SN2 mechanism on the σ λ deprotonated development of synthetic methods for the preparation of such intermediate) to yield the corresponding secondary phosphine compounds has acknowledged many discoveries, especially in oxides (SPOs) with high enantiospecificity,[13b,15a] as minor loss the last three decades (Figure 2). That is why this review aims of optical activity is usually observed. Our group has shown to present the recent developments in the synthesis of P-stereo- that these SPOs could be converted to either enantiopure phos- genic molecules. It will cover the following approaches: phinous acid-boranes[15b] or secondary phosphine-boranes.[15c] ● Via a chiral auxiliary bound to the P atom 1 can also be functionalized in the presence of carbonyl electro- ● Via a chiral stoichiometric reagent philes[13c,14] to generate the corresponding hydroxyalkyl phos- ● Via catalytic enantioselective reactions phinates with high diastereomeric ratios. ● Via semi-preparative chiral separation The palladium-catalyzed Markovnikov hydrophosphination