Synthesis and chemistry of a new P-N chelating ligand; (R) and (S)-6-(2′-diphenylphosphino-1′-naphthyl)phenanthridine

Valk, Jean-Marc; Claridge, Timothy D. W.; Brown, John M.; Hibbs, David E.; Hursthouse, Michael B.

doi:10.1016/0957-4166(95)00341-l

Cited by 79 publications

(36 citation statements)

References 24 publications

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“…This observation led to the design and synthesis of PHENAP (448), the phenanthridine analogue of QUINAP (441). [168] Ligand 448 was also tested in both palladium-catalysed allylic alkylation, giving slightly lower enantioselectivities than QUINAP, and the rhodium-catalysed hydroborations, Table 43, entries 2 and 3, and Table 42, entries 16 and 17. [169] Another isoquinoline type ligand, the 1-methyl-2-diphenylphosphino-3-(1'-isoquinolyl)indole (449) was …”

Section: Imidazoline N Donormentioning

confidence: 99%

The Development of Bidentate P,N Ligands for Asymmetric Catalysis

2004

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In this review, an attempt is made to systemise the ro √ le which bidentate phosphinamine (P,N) ligands play in asymmetric catalysis. The ligands will be classified, not by the reaction to which their metal complexes have been applied, but by the nature of their donor atoms. In this manner the development of ligand architectural design can be more easily monitored. The asymmetric transformations to which metal complexes of these ligands have been applied include among others, palladium-catalysed allylic substitutions, copper-catalysed 1,4-additions to enones and rhodiumcatalysed hydroboration of vinylarenes. Excellent enantioselectivities, regioselectivities and reactivities have been achieved in each of these processes.

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Section: Imidazoline N Donormentioning

confidence: 99%

The Development of Bidentate P,N Ligands for Asymmetric Catalysis

2004

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“…PHENAP (87) was prepared and resolved [115] in a similar manner to QUINAP (82) and tested in asymmetric rhodium-catalysed hydroboration-oxidations, [116] Table 11, entries 22 -25. Regioselectivities were on a par with QUINAP (82).…”

Section: Axial Chiralitymentioning

confidence: 99%

The Development of Enantioselective Rhodium-Catalysed Hydroboration of Olefins

Carroll

O’Sullivan

Guiry

2005

Advanced Synthesis & Catalysis

333

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Rhodium-catalysed enantioselective hydroboration of olefins is a valuable synthetic transformation, typically employing a chiral catalyst and an achiral borane source. The pertinent chemo-, regio-and enantioselectivity issues of this reaction are discussed. However, the main emphasis of this review is on the evolution of catalytic asymmetric hydroboration. This has primarily relied upon the development and application of chiral bidentate P,P and P,N ligands which have exhibited varying degrees of success in this transformation.

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“…This fi nding led to the design by Brown of the vaulted analogue PHENAP (58) (Figure 3.4 ), where the donor nitrogen atom is part of a phenanthridine unit. PHENAP (58) was prepared and resolved in a similar manner to QUINAP (52) and tested in asymmetric rhodium -catalyzed hydroboration -oxidations [54,55] . Regioselectivities were on a par with QUINAP (52) .…”

Section: Selectivity Of Metal-catalyzed Hydroboration 75mentioning

confidence: 99%

The Development and Application of Rhodium‐Catalyzed Hydroboration of Alkenes

Coyne

Guiry

2008

Modern Reduction Methods

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3.1 IntroductionHydroboration, the addition of a boron -hydrogen bond across an unsaturated moiety, was fi rst discovered by H. C. Brown in 1956 [1] . Usually the reaction does not require a catalyst and the borane reagent, most commonly diborane (B 2 H 6 ) or a borane adduct (BH 3 · THF), reacts rapidly at room temperature to afford, after oxidation, the anti -Markovnikov alkene hydration product. However, when the boron of the hydroborating agent is bonded to heteroatoms, as is the case in catecholborane (1,3,2 -benzodioxaborole) the electron density at boron is increased and elevated temperatures are needed for hydroboration to occur [2,3] .The development of a catalytic hydroboration process was aided by the observation of Kono and Ito in 1975 that Wilkinson ' s catalyst [Rh(PPh 3 ) 3 Cl] undergoes oxidative addition when treated with catecholborane (2) , Scheme 3.1 [4] . Subsequently, Westcott et al. reported the isolation of the oxidative addition adduct with the tri -isopropylphosphine derivative and its characterization by X -ray crystallography [5] . However, it was another decade before the idea of developing a rhodiumcatalyzed olefi n hydroboration process came to fruition with the fi rst examples reported by M ä nnig and N ö th [6] .The conversion of an alkene (1) into an organoborane intermediate (3) has made this a valuable synthetic technique, particularly since the development of enantioselective variants [7, 8] . They serve as synthons for numerous functional groups [9] and are often subject to a consecutive carbon -oxygen [10] , carbon -carbon [11 -13] boron -carbon [14] , boron -chlorine [5] , carbon -nitrogen [15] and other bondforming reactions, Scheme 3.2 . These and other approaches toward extending the synthetic scope of catalytic asymmetric hydroboration have been the subject of recent excellent reviews [16 -18] . Many metals including nickel [19] , ruthenium [20] , iridium [21] , lanthanum [22] , titanium [23] and zirconium [24] have been employed in this transformation with varying degrees of success, although rhodium has remained the metal of choice for transition metal hydroboration.

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Synthesis and chemistry of a new P-N chelating ligand; (R) and (S)-6-(2′-diphenylphosphino-1′-naphthyl)phenanthridine

Cited by 79 publications

References 24 publications

The Development of Bidentate P,N Ligands for Asymmetric Catalysis

The Development of Bidentate P,N Ligands for Asymmetric Catalysis

The Development of Enantioselective Rhodium-Catalysed Hydroboration of Olefins

The Development and Application of Rhodium‐Catalyzed Hydroboration of Alkenes

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