Phosphorus( III ) Ligands in Homogeneous Catalysis: Design and Synthesis -- Contents -- List of Contributors -- Preface -- 1 Phosphorus Ligand Effects in Homogeneous Catalysis and Rational Catalyst Design -- 1.1 Introduction -- 1.2 Properties of phosphorus ligands -- 1.2.1 Electronic ligand parameters -- 1.2.2 Steric ligand parameters -- 1.2.3 Bite angle effects -- 1.2.4 Molecular electrostatic potential (MESP) approach -- 1.3 Asymmetric ligands -- 1.4 Rational ligand design in nickel-catalysed hydrocyanation -- 1.4.1 Introduction -- 1.4.2 Mechanistic insights -- 1.4.3 Rational design -- 1.5 Conclusions -- References -- 2 Chiral Phosphines and Diphosphines -- 2.1 Introduction -- 2.1.1 Early developments -- 2.2 Chiral chelating diphosphines with a linking scaffold -- 2.2.1 Building chiral backbones from naturally available materials -- 2.2.2 Design and synthesis of chiral backbones -- 2.2.3 Synthesis from optical resolution of phosphine precursors or intermediates -- 2.3 Chiral atropisomeric biaryl diphosphines -- 2.3.1 Synthesis of BINAP and its derivatives -- 2.3.2 Synthesis of atropisomeric biaryl ligands -- 2.3.3 General strategies of synthesizing of atropisomeric biaryl ligands -- 2.4 Chiral phosphacyclic diphosphines -- 2.4.1 Fundamental discovery and syntheses of BPE and DuPhos -- 2.4.2 Design and synthesis of bisphosphetanes -- 2.4.3 Design and synthesis of bisphospholanes -- 2.4.4 Design and synthesis of bisphospholes -- 2.4.5 Design and synthesis of bisphosphinanes -- 2.4.6 Design and synthesis of bisphosphepines -- 2.4.7 Summary of synthetic strategies of phosphacycles -- 2.5 P-stereogenic diphosphine ligands -- 2.6 Experimental procedures for the syntheses of selected diphosphine ligands -- 2.6.1 Synthesis procedure for DIOP* ligand -- 2.6.2 Synthesis procedure of SDP ligands -- 2.6.3 Synthesis procedure of (R,R)-BICP.

2.6.4 Synthesis procedure of SEGPHOS -- 2.6.5 Synthesis procedure of Ph-BPE -- 2.6.6 Synthesis procedure of TangPhos -- 2.6.7 Synthesis procedure of Binaphane -- 2.7 Concluding remarks -- References -- 3 Design and Synthesis of Phosphite Ligands for Homogeneous Catalysis -- 3.1 Introduction -- 3.2 Synthesis of phosphites -- 3.2.1 Monophosphites -- 3.2.2 Diphosphite ligands -- 3.2.3 Triphosphites -- 3.3 Highlights of catalytic applications of phosphite ligands -- 3.3.1 Hydrogenation reactions -- 3.3.2 Functionalization of alkenes: hydroformylation and hydrocyanation -- 3.3.3 Addition of nucleophiles to carbonyl compounds and derivatives -- 3.3.4 Allylic substitution reactions -- 3.3.5 Miscellaneous reactions -- 3.4 General synthetic procedures -- 3.4.1 Symmetrically substituted phosphites -- 3.4.2 Nonsymmetrically substituted phosphites -- 3.4.3 Phosphites bearing dioxaphospho-cyclic units -- References -- 4 Phosphoramidite Ligands -- 4.1 Introduction -- 4.1.1 History -- 4.2 Synthesis of phosphoramidites -- 4.3 Reactivity of the phosphoramidites -- 4.4 Types of phosphoramidite ligands -- 4.4.1 Acyclic monodentate phosphoramidites -- 4.4.2 Cyclic monodentate phosphoramidites based on diols -- 4.4.3 Cyclic phosphoramidites based on amino alcohols -- 4.4.4 Bis-phosphoramidites -- 4.4.5 Mixed bidentate ligands -- 4.4.6 Polydendate phosphoramidites -- 4.5 Conclusion -- 4.6 Synthetic procedures -- References -- 5 Phosphinite and Phosphonite Ligands -- 5.1 Introduction -- 5.2 General methods for synthesis of complexes -- 5.3 Syntheses and applications of phosphinite ligands -- 5.3.1 Early studies -- 5.3.2 Phosphinite ligands from carbohydrates -- 5.3.3 Phosphinite ligands from other alcohols -- 5.3.4 Phosphine-phosphinite and amine-phosphinite ligands -- 5.3.5 Phosphinites from amines, amino alcohols, and amino acids.

5.3.6 Bisphosphinite ligands with other scaffoldings -- 5.3.7 1,1′-Diaryl-2,2′-phosphinites and dynamic conformational control in asymmetric catalysis -- 5.3.8 Monophosphinite ligands -- 5.3.9 Hybrid ligands containing phosphinites -- 5.4 Synthesis and applications of phosphonite ligands -- 5.4.1 Early studies -- 5.4.2 Phosphonites from TADDOL and related compounds -- 5.4.3 Phosphonites derived from 2,2′-hydroxybiaryls and related compounds -- 5.4.4 Phosphine-phosphonite ligands -- 5.4.5 Phosphonites with paracyclophane backbone -- 5.4.6 Phosphonites with a spirobisindane backbone -- 5.4.7 Miscellaneous phosphonite ligands -- 5.4.8 Development of phosphonite ligands for industrially relevant processes -- 5.4.9 Use of the phosphonite functionality to synthesize other ligands -- 5.5 Experimental procedures for the syntheses of prototypical phosphinite and phosphonite ligands -- 5.5.1 Phosphinite ligands -- 5.5.2 Phosphonite ligands -- 5.6 Acknowledgments -- Abbreviations -- References -- 6 Mixed Donor Ligands -- 6.1 Introduction: general design principles -- 6.2 Synthesis of bidentate P,X-ligands -- 6.2.1 P,N-ligands -- 6.2.2 P,O-ligands -- 6.2.3 P,S-ligands -- 6.2.4 P,C-ligands -- 6.3 Conclusion -- 6.4 Experimental procedures -- 6.4.1 Synthesis of PHOX ligand -- 6.4.2 Synthesis of NeoPHOX ligand -- References -- 7 Phospholes -- 7.1 Introduction -- 7.2 Creation of phospholes for use as ligands -- 7.2.1 Reactions of phosphorus dihalides with metallated dienes -- 7.2.2 Reactions of phosphorus dihalides with dienes -- 7.2.3 Michael addition of primary phosphines to dienes -- 7.3 Postsynthetic functionalisation -- 7.3.1 Functionalisation at phosphorus -- 7.3.2 At phosphorus: use of electrophiles -- 7.3.3 At phosphorus: use of nucleophiles and aromatics -- 7.3.4 At carbon: elaboration about the phosphole nucleus -- 7.4 Phosphole coordination chemistry.

7.5 Phospholes in catalysis -- 7.6 Experimental procedures -- References -- 8 Phosphinine Ligands -- 8.1 Introduction -- 8.2 Ligand properties -- 8.2.1 Electronic properties -- 8.2.2 Structural characteristics and steric properties -- 8.2.3 Reactivity of phosphinines -- 8.3 Synthesis of Phosphinines -- 8.3.1 O+/P exchange reaction -- 8.3.2 Tin route -- 8.3.3 [4 + 2] cycloaddition reactions -- 8.3.4 Ring expansion methods -- 8.3.5 Metal-mediated functionalizations -- 8.4 Coordination chemistry -- 8.5 Reactivity of transition metal complexes -- 8.6 Application of phosphinines in homogeneous catalysis -- 8.7 Experimental procedure for the synthesis of selected phosphinines -- References -- 9 Highly Strained Organophosphorus Compounds -- 9.1 Introduction -- 9.2 Three-membered rings -- 9.3 Rearrangements -- 9.4 Homogeneous catalysis -- 9.5 Conclusions -- 9.6 Experimental procedures -- 9.6.1 Synthesis of BABAR-Phos 49a (R = i-Pr) -- 9.6.2 Synthesis of BABAR-Phos 49b (R = 3,5-(CF3)2C6H3) -- References -- 10 Phosphaalkenes -- 10.1 Introduction -- 10.1.1 Frontier molecular orbitals of phosphaalkenes -- 10.2 Synthesis of phosphaalkenes -- 10.2.1 Diphosphinidenecyclobutene (DPCB) synthesis (P,P chelates) -- 10.2.2 Bidentate-chelating P,P phosphaalkene ligands -- 10.2.3 Phosphaalkenes capable of P,N-chelation to metals -- 10.2.4 P,X achiral phosphaalkene ligands (X=P, O, S) -- 10.2.5 Synthesis of enantiomerically pure P,X ligands (X=P, N) -- 10.3 Catalysis with phosphaalkene ligands -- 10.3.1 Ethylene polymerization -- 10.3.2 Cross-coupling reactions -- 10.3.3 Hydro- and dehydrosilylation -- 10.3.4 Hydroamination and hydroamidation -- 10.3.5 Isomerization reactions -- 10.3.6 Allylic substitution -- 10.3.7 Asymmetric catalysis -- 10.4 Concluding remarks -- 10.5 Experimental procedures for representative ligands -- 10.5.1 Synthesis of DPCB.

10.5.2 Synthesis of PhAk-Ox -- 10.6 Acknowledgments -- References -- 11 Phosphaalkynes -- 11.1 Introduction -- 11.2 General experimental -- 11.3 Preparation of PCtBu -- 11.3.1 Tris(trimethylsilyl)phosphine, P(SiMe3)3 -- 11.3.2 tert-butylphosphaalkene, Me3SiP = C(OSiMe3)tBu (systematic name [2,2-dimethyl-1-(trimethylsiloxy)propylidene]-(trimethylsilyl) phosphine) -- 11.3.3 tert-butylphosphaalkyne, systematic name (2,2-dimethylpropylidyne)phosphine -- tBuC≡P -- 11.4 Adamanylphosphaalkyne, AdC≡P -- 11.4.1 Adamant-1-yl(trimethylsiloxy)methylidene (trimethylsilyl) phosphine -- 11.4.2 (Adamant-1-ylmethylidyne)phosphine -- 11.5 Mesitylphosphaalkyne, MesC≡P -- 11.5.1 Preparation of potassium bis(trimethylsilyl)phosphide {KP(SiMe3)2} -- 11.5.2 Mesityl(trimethylsiloxy)methylene trimethylsilylphosphine -- 11.5.3 Mesitylphosphaalkyne -- 11.6 Phospholide anions -- 11.6.1 Preparation of Cp2Zr(PCtBu)2 -- 11.6.2 Preparation of ClP(PCtBu)2 -- 11.6.3 Preparation of the triphospholide anion and derivation to give the triphenylstannylphosphole -- 11.6.4 Preparation of Cl3P3(CtBu)2 -- 11.6.5 Preparation of the triphospholide anion -- 11.7 1,3,5-Triphosphabenzene -- 11.7.1 Preparation of Cl3VNtBu -- 11.7.2 Preparation of 1,3,5-triphospabenzene -- P3(CtBu)3 -- References -- 12 P-chiral Ligands -- 12.1 Introduction -- 12.2 Designing P-chiral ligands using alcohols as chiral auxiliaries -- 12.3 Designing P-chiral ligands using amino alcohols as chiral auxiliaries -- 12.3.1 Synthesis starting from tricoordinated 1,3,2-oxazaphospholidines -- 12.3.2 Synthesis starting from tetracoordinated 1,3,2-oxazaphospholidines -- 12.3.3 Synthesis starting from 1,3,2-oxazaphospholidine borane complexes -- 12.4 Designing of P-chiral ligands using amines as chiral auxiliaries -- 12.4.1 Sparteine as chiral auxiliary -- 12.4.2 α-Arylethylamines as chiral auxiliaries -- 12.5 Conclusion.

12.6 Experimental procedures.