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Design of P-Chirogenic Aminophosphine-Phosphinite

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Design of P-Chirogenic Aminophosphine-Phosphinite Design of P-Chirogenic Aminophosphine-Phosphinite (AMPP*) Ligands at both Phosphorus Centers: Origin of Enantioselectivities in Pd-Catalyzed Allylic Reactions Antonin Jaillet, Christophe Darcel, Jérôme Bayardon, Adrien Schlachter, Christine Salomon, Yoann Rousselin, Pierre D Harvey, Sylvain Jugé To cite this version: Antonin Jaillet, Christophe Darcel, Jérôme Bayardon, Adrien Schlachter, Christine Salomon, et al.. Design of P-Chirogenic Aminophosphine-Phosphinite (AMPP*) Ligands at both Phosphorus Cen- ters: Origin of Enantioselectivities in Pd-Catalyzed Allylic Reactions. Journal of Organic Chemistry, American Chemical Society, 2020, 85 (22), pp.14391-14410. 10.1021/acs.joc.0c00536. hal-02635117 HAL Id: hal-02635117 https://hal-univ-rennes1.archives-ouvertes.fr/hal-02635117 Submitted on 28 May 2020 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. Page 1 of 95 The Journal of Organic Chemistry 1 Design of P-Chirogenic Aminophosphine-Phosphinite 2 3 4 5 (AMPP*) Ligands at both Phosphorus Centers: Origin of 6 7 8 9 10 Enantioselectivities in Pd-Catalyzed Allylic Reactions 11 12 13 14 Antonin Jaillet,a§ Christophe Darcel,b Jérôme Bayardon,a Adrien Schlachter,c Christine 15 16 17 18 Salomon,a Yoann Rousselin,a Pierre Harvey,c and Sylvain Jugé*a 19 20 21 22 23 24 25 26 a Université de Bourgogne-Franche-Comté, Institut de Chimie Moléculaire (ICMUB-OCS, 27 28 29 30 UMR-CNRS 6302), BP 47870, 21078 Dijon Cedex, France 31 32 33 34 35 b Université de Rennes, Institut des Sciences Chimiques de Rennes (ISCR, UMR-CNRS 36 37 38 6626), 35000 Rennes, France 39 40 41 42 43 c Université de Sherbrooke, Département de Chimie, Sherbrooke, Québec, Canada 44 45 46 J1K2R1 47 48 49 50 51 52 53 54 Accepted Manuscript 55 56 57 58 59 60 1 ACS Paragon Plus Environment The Journal of Organic Chemistry Page 2 of 95 1 RECEIVED DATE (to be automatically inserted after your manuscript is accepted if 2 3 4 required according to the journal that you are submitting your paper to) 5 6 7 8 9 CORRESPONDING AUTHOR FOOTNOTE 10 11 12 [*] To whom correspondence should be addressed. -mail: [email protected], 13 14 15 Tel: +33 (0)3 80 39 61 13. 16 17 18 19 20 21 22 23 TABLE OF CONTENTS/ABSTRACT GRAPHIC 24 25 26 27 28 N O phosphinyl migration 29 BH3 R R1 R Pd-catalyzed 1 P PPh2 1 30 R1 P P R R Ph2P P R asymmetric N O 31 R N DABCO MeNH O Me or MeN O reactions Me OH 32 50°C e.e. up to 33 Me Ph Me Ph 91% (R) Me overnight Me Ph Ph or 95% (S) 34 55-88% yields AMPP* ligands (29 examples) 35 Manuscript 36 37 38 ABSTRACT 39 40 We have recently patented an unprecedented stereospecific N→O phosphinyl migration 41 42 43 44 process which transforms P-chirogenic aminophosphines into phosphinites. A fine design 45 46 47 of aminophosphine phosphinite ligands (AMPP*) derived from ephedrine and bearing a P- 48 49 50 51 chirogenic center either at the aminophosphine or phosphinite moiety, was performed. The 52 53 54 synthesisAccepted of AMPP* ligands with P-chirogenic aminophosphine moiety was based on the 55 56 57 58 well-established stereospecific reaction of oxazaphospholidine-borane with organolithium 59 60 2 ACS Paragon Plus Environment Page 3 of 95 The Journal of Organic Chemistry 1 reagents, followed by trapping with a chlorophosphine and borane decomplexation. 2 3 4 Concurrently, the preparation of AMPP* ligands with P-chirogenic phosphinite moiety were 5 6 7 8 performed by N→O phosphinyl migration of aminophosphines borane by heating at 50 °C 9 10 11 with DABCO, and then reaction with chlorophosphines. AMPP* ligands were studied in 12 13 14 15 palladium-catalyzed asymmetric allylic alkylations, leading to enantioselectivities from 91% 16 17 18 (R) to 95% e.e. (S). X-ray crystallographic data for relevant Pd-AMPP* complexes and 19 20 21 22 computer modeling explained the origin of the enantioselectivities based on MO 23 24 25 interactions of most stable conformers with nucleophiles. 26 27 28 29 KEYWORDS 30 31 32 P-Chirogenic ligands / Asymmetric catalysis / Palladium / Allylic substitution / 33 34 35 Manuscript 36 Aminophosphine-phosphinites / Phosphorus rearrangement/ DFT-computation 37 38 39 40 41 42 43 44 45 1. INTRODUCTION 46 47 48 The chirality in phosphines used in enantioselective metal-catalyzed or 49 50 51 1-3 52 organocatalyzed reactions has overwhelmingly been located on the carbon skeleton. If 53 54 Accepted 55 the efficiency of P-chirogenic ligands is also documented,4 the design of chiral ligands at 56 57 58 59 the phosphorus centers has largely been neglected due to the lack of versatile methods to 60 3 ACS Paragon Plus Environment The Journal of Organic Chemistry Page 4 of 95 1 efficiently design series of catalysts and to obtain their enantiopure stereoisomers. 2 3 4 Although the use of P-chirogenic compounds in organocatalyzed asymmetric reactions is 5 6 7 3 5 8 also known for several decades, their applications also recently increased significantly. 9 10 11 Consequently and unsurprisingly, the design of P-chirogenic compounds (and not only 12 13 14 15 phosphines) is still a very active research area for the development of enantioselective 16 17 18 catalyzed reactions. So far, the stereoselective synthesis of P-chirogenic 19 20 21 22 organophosphorus compounds was usually achieved by P-C bond formation. This was 23 24 25 done using a limited number of P-chirogenic tetracoordinated building blocks, such as t- 26 27 28 29 butylmethylphosphine-borane, secondary phosphine-oxide or phosphinous-borane 30 31 32 derivatives.4 33 34 35 Manuscript 36 Chiral aminophosphine phosphinites (AMPP) such as 1-8, represent a large family of 37 38 39 readily available bidendate ligands in asymmetric catalysis (Chart 1).6 These ligands are 40 41 42 43 obtained from the reaction between two equivalents of Ph2PCl or (c-pent)2PCl with 44 45 46 commercially available amino alcohols such as ephedrine, threoninol,7a prolinol,7b valinol,7c 47 48 49 propranolol,7d 1,2-diphenyl aminoethanol,7e,f 2-indoline-methanol7g,h or 50 51 52 53 azabicyclo[2.2.1]hept-3-ylmethanol.7i AMPP ligands 2-8 are excellent for the asymmetric 54 Accepted 55 56 hydrovinylation of cyclohexadiene,7a [2+2+2] cycloaddition,7b,c hydrogenation of C=C7d-f,i or 57 58 59 60 4 ACS Paragon Plus Environment Page 5 of 95 The Journal of Organic Chemistry 7g,h 1 C=O, respectively. Enantioselectivities up to 99% e.e. using Ni-, Co- or Rh-based 2 3 4 complexes have been reached. 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Chart 1. Representative Chiral Aminophosphine-Phosphinite (AMPP) ligands 24 25 26 27 The EPHOS ligand 1 derived from (-)-ephedrine, described in pioneering works by B. 28 29 30 8a 8b 31 Petit and G. Buono, led to moderate enantioselectivities in asymmetric hydrogenation, 32 33 34 hydroformylation,8c,d hydrosilylation8e and allylation8f catalyzed by Pt-, Rh- or Pd-complexes, 35 Manuscript 36 37 38 respectively. During the past decade, we and Vogt group have independently described the 39 40 41 synthesis of two series of modified EPHOS ligands 13 and 16 with P-chirogenic phosphorus 42 43 44 centers (Scheme 1).9,10 45 46 47 48 Scheme 1. Stereoselective Synthesis of Modified EPHOS with P-chirogenic P-Centers 49 50 51 52 53 54 Accepted 55 56 57 58 59 60 5 ACS Paragon Plus Environment The Journal of Organic Chemistry Page 6 of 95 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 So far, a large series of P-chirogenic modified EPHOS ligands 13 (AMPP*) has been 25 26 27 28 synthesized from the oxazaphospholidine-borane (-)- or (+)-10. They were derived from 29 30 31 (+)- or (-)-ephedrine 9 based on a well-established methodology (Scheme 1).9,10 Thus, the 32 33 34 borane complex (-)-10 reacted with organolithium reagents (R1Li) to afford the lithium salts 35 Manuscript 36 37 38 [11] by a ring opening reaction upon P-O bond cleavage. The salts [11] were successively 39 40 41 trapped with a chlorophosphine R' PCl then with borane to produce the AMPP*-diborane 42 2 43 44 45 complexes 12, and then isolated as air-stable and storable compounds (Scheme 1a). The 46 47 48 free AMPP* 13 finally obtained after borane decomplexation of their corresponding 49 50 51 52 diborane complexes 12 with DABCO, yielded up to 73% from ephedrine (Scheme 1a). This 53 54 Accepted 55 methodology permitted to synthesize numerous P-chirogenic AMPP* ligands 13 with R1 = 56 57 58 59 alkyl, cycloalkyl, aryl, bisaryl, heteroaryl or ferrocenyl and R' = phenyl-, -naphtyl- or 3,5- 60 6 ACS Paragon Plus Environment Page 7 of 95 The Journal of Organic Chemistry 1 xylyl-substituents on the aminophosphine and phosphinite moieties, respectively (Scheme 2 3 4 1a).9,10 Similarly, the AMPP* ligands 13u-w bearing o-biphenyl, calix[4]arenyl and 1,1'- 5 6 7 8 binaphth-2-yl substituents on the P-chirogenic aminophosphine moiety were prepared 9 10 11 using the same methodology, but starting from (-)-ephedrine 9 (Scheme 2 and Supporting 12 13 14 9c 15 Information, SI).
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