Enantioselective Synthesis of P‐Stereogenic Alkynylphosphine Oxides by Rh‐Catalyzed [2+2+2] Cycloaddition

Nishida, Goushi; Noguchi, Keiichi; Hirano, Masao; Tanaka, Ken

doi:10.1002/anie.200800144

Cited by 118 publications

(45 citation statements)

References 57 publications

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“…[26] The selective desymmetrization observed could be explained in terms of strong steric effects being present between the alkynyl group on the oxide and the phosphorus substituents of the chiral ligand before the final alkyne insertion in the corresponding rhodacyclopentadiene. Indeed, stereogenic phosphorus atoms are obtained as the result of the desymmetrization of symmetrical dialkynylphosphine oxides through a rhodium-catalyzed [2+2+2] cycloaddition pathway (Scheme 11).…”

Section: Miscellaneous Intermolecular [2+2+2] Cycloadditionsmentioning

confidence: 99%

Recent Advances in Stereoselective [2+2+2] Cycloadditions

2014

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The [2+2+2] cycloaddition reaction is considered one of the most efficient methods for the rapid and straightforward preparation of complex polycyclic (and heterocyclic) compounds in a highly selective and atom‐economical fashion. Over the last half‐century, remarkable advances in terms of chemo‐ and regioselectivities have been realized, endowing this reaction with attractive features as a key step in the synthesis of various biologically active molecules and materials. The development of stereoselective methodologies is more recent. In this field, asymmetric transition‐metal catalysis has emerged as the most convenient tool with which to perform these [2+2+2] cycloadditions in their enantio‐ and diastereoselective variants. All the catalytic systems that have been developed so far are based on very close association of a transition metal (Co, Ni, Ir, Rh, ...) with a chiral ligand. The success of these reactions is then related to the reaction pattern involved (inter‐ and intramolecular), implying an efficient substrate/active species interaction. Thus, judicious design both of chiral ligands and of unsaturated substrates is necessary. In light of these aspects, numerous stereoselective cycloadditions have been reported; these allow the construction in one‐step fashion of central, axial, planar, and helical chiralities. This review details the recent advances in this area, with specific attention to catalysts and reaction scope.

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Section: Miscellaneous Intermolecular [2+2+2] Cycloadditionsmentioning

confidence: 99%

Recent Advances in Stereoselective [2+2+2] Cycloadditions

2014

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“…Preliminary studies have shown that these monophosphines are highly efficient ligands that either rival or outperform their biaryl-based counterparts in palladium-catalyzed Suzuki-Miyaura and Buchwald-Hartwig cross-couplings 50,51 , a host of gold(I)-catalyzed intramolecular cycloisomerizations [57][58][59] , as well as in the ruthenium-catalyzed direct ortho arylation of 2-phenylpyridine and N-phenylpyrazole with aryl chlorides 60 . In addition, biaryl monophosphines have also been prepared by rhodium-catalyzed [2 + 2 + 2] cycloaddition [61][62][63] and Diels-Alder cycloaddition extrusion 64 .…”

Section: Simon Doherty and Catherine H Smythmentioning

confidence: 99%

Synthesis and resolution of the biaryl-like diphosphine (S)-Me2-CATPHOS, preparation of a derived rhodium precatalyst and applications in asymmetric hydrogenation

Doherty

Smyth

2012

Nat Protoc

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This protocol describes the synthesis of a representative example of the enantiopure biaryl-like CATPHOS class of diphosphines, (S)-9,9'-dimethyl-9,9',10,10'-tetrahydro-9,10,9',10'-biethenobianthracene-11,11'-bis(diphenylphosphino)-12,12'-diyl ((S)-Me(2)-CATPHOS), and its derived cationic rhodium-based hydrogenation precatalyst. The C(2)-symmetric framework of Me(2)-CATPHOS is the result of a regioselective Diels-Alder cycloaddition between 1,4-bis(diphenylphosphinoyl)buta-1,3-diyne and 9-methylanthracene, such that the bulky methyl-substituted bridgehead carbon atoms are attached to C2 and C3 of the 1,3-butadiene tether. Enantiopure Me(2)-CATPHOS is obtained in an operationally straightforward three-step procedure and isolated in ∼50-60% overall yield and <99% enantiopurity, after diastereoselective resolution with (2R,3R)-(-)-2,3-O-dibenzoyltartaric acid. The derived rhodium complex forms a highly effective catalyst for the asymmetric hydrogenation of a range of dehydroamino acid derivatives, as well as (E)-β-aryl-(enamido)phosphonates, giving ee values in excess of 99%, the highest to be reported for the latter class of substrate. The total time required for the synthesis of (S)-Me(2)-CATPHOS, including resolution, reduction and crystallizations, is 130 h and preparation of the corresponding rhodium precatalyst requires an additional 24-26 h.

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“…The cationic chiral rhodium(I)‐catalyzed cycloaddition was applied for desymmetrization of dialkynylphosphine oxide 83 with 1,6‐diyne 19 (entry 4) [18]. The P‐stereogenic alkynylphosphine oxide 84 was obtained in high yield and high enantiomeric excess.…”

Section: Construction Of Central Chiralitymentioning

confidence: 99%