1-R-1, 3λ3-azaphosphole

Märkl, Gottfried; Dorfmeister, G.

doi:10.1016/s0040-4039(00)84967-9

Cited by 37 publications

(5 citation statements)

References 16 publications

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“…100 Building off work forming 1,3-azaphospholes, they converted a series of triaryl-1,3-azapyrilium tetrafluoroborate salts 130 into the respective 1,3λ 3 -azaphosphinine products 131 in the presence of tris(trimethysilyl)phosphane in modest yields (Scheme 50). 101,102…”

Section: 3-azaphosphininesmentioning

confidence: 99%

“…100 Building off work forming 1,3-azaphospholes, they converted a series of triaryl-1,3-azapyrilium tetrafluoroborate salts 130 into the respective 1,3l 3 azaphosphinine products 131 in the presence of tris(trimethysilyl)phosphane in modest yields (Scheme 50). 101,102 Treating the 2,4,6-triphenyl derivative 131a with phenyl lithium added a phenyl group to the phosphorus center to afford phosphinyl anion 132, and subsequent protonation by water gave non-aromatic 2,3-dihydro-1,3l 3 -azaphosphinine 133 (Scheme 51). Alternatively, 131a could react as a diene in a [4+2] cycloaddition with either DMAD or methyl propiolate followed by cycloreversion to extrude benzonitrile, forming phosphinines 134a or 134b, respectively, in good yields.…”

Section: 3-azaphosphininesmentioning

confidence: 99%

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Azaphosphinines and their derivatives

McNeill,

Bard,

Johnson

et al. 2023

Chem. Soc. Rev.

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Section: 3-azaphosphininesmentioning

confidence: 99%

Section: 3-azaphosphininesmentioning

confidence: 99%

Azaphosphinines and their derivatives

McNeill,

Bard,

Johnson

et al. 2023

Chem. Soc. Rev.

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“…However, the regioselectivities of Münchnone cycloadditions with alkynes are often found to be poor. Whereas cycloadditions with electronically biased dipolarophiles such as imines, aldehydes, and phosphaalkenes do give the predicted cycloadduct with high selectivity (e.g., Scheme a and b), cycloadditions with polarized alkynes ,, and alkenes , frequently lead to mixtures of regioisomers (e.g., Scheme c–e). A number of attempts have been made to understand this selectivity , and have proposed explanations based on steric influences and cycloaddition asynchronicity.…”

Section: Introductionmentioning

confidence: 99%

Modular Mesoionics: Understanding and Controlling Regioselectivity in 1,3-Dipolar Cycloadditions of Münchnone Derivatives

et al. 2013

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1,3-Dipolar cycloadditions of mesoionic 1,3-dipoles (Münchnones, imino-Münchnones, and phospha-Münchnones) with alkynes offer versatile, modular synthetic routes to pyrroles. Reactivity and regioselectivity differ markedly for different members of this series, and we report here the first general rationale for differences in reactivity by means of a systematic investigation of 1,3-dipolar cycloadditions involving electron-poor and electron-rich alkynes. Competition kinetic measurements indicate that Münchnones and phospha-Münchnones are nucleophilic 1,3-dipoles that react most rapidly with electron-poor alkynes. However, the regioselectivities of cycloadditions are found to undergo an inversion as a function of alkyne ionization potential. The exact point at which this occurs is different for the two dipoles, allowing rational control of the pyrrole formed. The origins of these reactivities and regioselectivities are examined computationally. Frontier molecular orbital predictions are found not to be accurate for these reactions, but transition state calculations give correct predictions of reactivity and selectivity, the origins of which can be analyzed using the distortion/interaction model of reactivity. Cycloadditions with electron-poor alkynes are shown to favor the regioisomer that has either the most favorable TS interaction energy (Münchnones or imino-Münchnones) or the smallest TS distortion energy (phospha-Münchnones). Cycloadditions with more electron-rich aryl-substituted alkynes, on the other hand, generally favor the regioisomer that has the smaller TS distortion energy. These insights delineate the synthetically important distinctions between Münchnones and phospha-Münchnones: phospha-Münchnones undergo highly regioselective cycloadditions with electron-poor alkynes that do not react selectively with Münchnones, and the reverse is true for cycloadditions of Münchnones with electron-rich alkynes.

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“…Phosphorus compounds in low coordination states are of interest in terms of bonding nature, reactivity, and potential application as ligands for organometallic complexes. Such phosphorus functionality as P C< [1], P P [2], and C≡P [3,4] has been available primarily through the use of bulky substituents (e.g., t-butyl, mesityl, and 2,4,6-tri-tbutylphenyl or "super mesityl = Mes * ") [1][2][3][4].…”

Section: Introductionmentioning

confidence: 99%