1‐Alkynylphosphines and Their Derivatives as Key Starting Materials in Creating New Phosphines

Kondoh, Azusa; Yorimitsu, Hideki; Oshima, Koichiro

doi:10.1002/asia.200900447

Cited by 41 publications

(7 citation statements)

References 118 publications

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“…Propargyl organophosphorus compounds present a unique interest from a synthetic point of view due to their ability to create new phosphines [ 48 ] or to be involved in various reactions (e.g., [2 + 3] cycloaddition) [ 49 – 50 ]. Moreover, propargyl compounds are known to undergo base catalyzed 1,3-prototropic rearrangments to the corresponding allenes [ 51 ], a highly usefull class of compounds [ 52 – 54 ].…”

Section: Resultsmentioning

confidence: 99%

Synthesis of γ-hydroxypropyl P-chirogenic (±)-phosphorus oxide derivatives by regioselective ring-opening of oxaphospholane 2-oxide precursors

Binyamin¹,

Meidan-Shani²,

Ashkenazi³

2015

Beilstein J. Org. Chem.

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SummaryThe synthesis of P-chirogenic (±)-phosphine oxides and phosphinates via selective nucleophilic ring opening of the corresponding oxaphospholanes is described. Two representative substrates: the phosphonate 2-ethoxy-1,2-oxaphospholane 2-oxide and the phosphinate 2-phenyl-1,2-oxaphospholane 2-oxide were reacted with various Grignard reagents to produce a single alkyl/aryl product. These products may possess further functionalities in addition to the phosphorus center such as the γ-hydroxypropyl group which results from the ring opening and π-donor moieties such as aryl, allyl, propargyl and allene which originates from the Grignard reagent.

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Section: Resultsmentioning

confidence: 99%

Synthesis of γ-hydroxypropyl P-chirogenic (±)-phosphorus oxide derivatives by regioselective ring-opening of oxaphospholane 2-oxide precursors

Binyamin¹,

Meidan-Shani²,

Ashkenazi³

2015

Beilstein J. Org. Chem.

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“…Alkynes are useful functional groups in synthesis owing to their application in a multitude of synthetic transformations. Enhanced reactivity as well as the biological significance makes heteroatom substituted alkynes such as ynamides and thioalkynes more important among alkynes . Hypercoordinate iodine reagents such as ethynylbenziodoxolone (EBX) act as excellent electrophilic alkyne transfer agents whereas in traditional methods alkynes are typically added as nucleophiles .…”

Section: Alkynylationmentioning

confidence: 99%

Hypercoordinate iodine(III) promoted reactions and catalysis: an update on current mechanistic understanding

Sreenithya

Surya

Sunoj

2017

WIREs Comput Mol Sci

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Mild and environment friendly hypercoordinate iodine compounds exhibit promising reactivities resembling that of transition metal catalysts. Hypercoordinate iodine reagents or catalysts are increasingly been employed in contemporary organic synthesis. However, mechanistic insights on such reactions continue to remain rather limited. Recent advances in the mechanistic understanding on a selected set of reactions involving hypercoordinate iodine form the main theme of this review. An overview of bonding, reactivity, and mechanistic insights on iodine(III) reactions such as α-functionalization of carbonyl compounds, alkynylation, amination, C H functionalization, phenol dearomatization, and trifluoromethylation have been described. In keeping with the current practices in mechanistic studies, we have maintained an interdisciplinary flavor in this compilation by providing a balanced view of computational and experimental understanding on the burgeoning domain of hypercoordinate iodine mediated reactions and catalysis. FIGURE 1 | Molecular orbital (MO) diagram for three-center-fourelectron (3c-4e) bond in hypercoordinate iodine compound RIL 2 . SCHEME 1 (a) General representation of α-tosyloxylation ketone catalyzed by Koser's reagent. (b) General mechanism for the α-tosyloxylation ketone. (c) Commonly employed iodoarenes in α-tosyloxylation. Overview wires.wiley.com/compmolsci SCHEME 2 (a) Effect of different substituents on the catalytic activity of iodoaryl in α-tosyloxylation. (b) Effect of different substituents on dihedral angle θ(C1-C2-I3-O4). (c) Formation of iodono intermediate 4 and the related ΔG rxn . WIREs Computational Molecular Science Hypercoordinate iodine(III) promoted reactions and catalysis Volume 7,

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“…Notably P-stereogenic alkynylphosphines were shown to induce excellent enantioselectivity in several asymmetric transition metal-catalyzed reactions [ 5 ]. Moreover the easy transformation of alkynylphosphines into valuable functionalized alkenyl mono- or di-phosphines through addition reactions on the triple bond was recently demonstrated [ 6 ]. These new applications as ligands for homogeneous catalysis and building blocks for organophosphorus chemistry have aroused the need for new general synthetic methods allowing the access to a broad substitution pattern.…”

Section: Introductionmentioning

confidence: 99%

Stoichiometric and Catalytic Synthesis of Alkynylphosphines

et al. 2012

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Alkynylphosphines or their borane complexes are available either through C–P bond forming reactions or through modification of the phosphorus or the alkynyl function of various alkynyl phosphorus derivatives. The latter strategy, and in particular the one involving phosphoryl reduction by alanes or silanes, is the method of choice for preparing primary and secondary alkynylphosphines, while the former strategy is usually employed for the synthesis of tertiary alkynylphosphines or their borane complexes. The classical C–P bond forming methods rely on the reaction between halophosphines or their borane complexes with terminal acetylenes in the presence of a stoichiometric amount of organometallic bases, which precludes the access to alkynylphosphines bearing sensitive functional groups. In less than a decade, efficient catalytic procedures, mostly involving copper complexes and either an electrophilic or a nucleophilic phosphorus reagent, have emerged. By proceeding under mild conditions, these new methods have allowed a significant broadening of the substituent scope and structure complexity.

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1‐Alkynylphosphines and Their Derivatives as Key Starting Materials in Creating New Phosphines

Cited by 41 publications

References 118 publications

Synthesis of γ-hydroxypropyl P-chirogenic (±)-phosphorus oxide derivatives by regioselective ring-opening of oxaphospholane 2-oxide precursors

Synthesis of γ-hydroxypropyl P-chirogenic (±)-phosphorus oxide derivatives by regioselective ring-opening of oxaphospholane 2-oxide precursors

Hypercoordinate iodine(III) promoted reactions and catalysis: an update on current mechanistic understanding

Stoichiometric and Catalytic Synthesis of Alkynylphosphines

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