The 3JCCNP Coupling Constants of Pentacoordinate Spirophosphorane Derivatives: As a Method to Assign Relative Configuration

Cao, Shuting; Zhou, Zhongfei; Dai, Wang; Zhao, Pei; Guo, Yating; Zhao, Yufen

doi:10.1080/10426507.2014.991824

Cited by 8 publications

(6 citation statements)

References 15 publications

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“…The absolute phosphorus configuration of product 2be was confirmed by X-ray structure analysis, and it was identified to be [Δ P , R C ] configuration (Table ). Although the single crystals of other products were not obtained, their phosphorus configuration could be presumed by the NMR method proposed by our group. , Therefore, the result of NMR and X-ray structure analysis testified the retention of phosphorus configuration in the diastereoselective addition reaction, and the main product from the addition reaction of AA-HSPs (Δ P ) was determined to be [Δ P , R C ] configuration. After the studies of the addition reaction of Val-HSP 1a (Δ P ) to aromatic aldehydes, the reaction of Ile-HSP 1b (Δ P ) was also investigated.…”

Section: Resultsmentioning

confidence: 97%

Investigation of the Asymmetric Addition Reactions Induced by Pentacoordinated Hydrospirophosphorane Substrate

et al. 2023

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Pentacoordinated bisaminoacyl hydrospirophosphoranes were first found to induce the asymmetric addition reactions as a novel chiral organic framework. Asymmetric addition reactions of bisaminoacyl hydrospirophosphoranes with aromatic aldehyde and in situ generated imine were investigated, and the corresponding α-hydroxyspirophosphonates and α-amino spirophosphonates were obtained. The addition reaction of hydrospirophosphoranes with ΔP configuration showed better stereoselectivity than that with ΛP configuration, not only for the addition reaction to aromatic aldehyde but also to in situ generated imine. Furthermore, the stereochemical mechanisms of asymmetric addition reactions induced by pentacoordinated hydrospirophosphorane were proposed by 31P NMR tracing experiment and X-ray diffraction analysis.

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Section: Resultsmentioning

confidence: 97%

Investigation of the Asymmetric Addition Reactions Induced by Pentacoordinated Hydrospirophosphorane Substrate

et al. 2023

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“…The coupling constant 3 J CCNP was reported to be very sensitive to the relative configurations of pentacoordinate phosphorus atoms. Usually, the configuration of isomer with large coupling constant 3 J CCNP , which signal of 31 P NMR appears in low field, is deduced to be Λ P configuration according to the rule reported, 3 J CCNP (Λ P ) ˃ 3 J CCNP (Δ P ) . In this regard, it was noted that the alkoxy spirophosphorane isomer 2a‐2 with coupling constant 3 J CCNP 6.3 Hz should be Λ P configuration, and the isomer 2a′‐2 with 3 J CCNP 3.8 Hz was presumed to be Δ P configuration.…”

Section: Resultsmentioning

confidence: 97%

Synthesis and Characterization of Alkoxy Spirophosphoranes Prepared from Hydrospirophosphoranes and Sodium Alcoholates

Dai

Liu

You

et al. 2015

Heteroatom Chemistry

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The Atherton–Todd‐type reaction of hydrospirophosphoranes (HSPs) and sodium alcoholates was investigated. Direct alkoxylation of HSPs was accomplished with sodium alcoholates in acetonitrile under nitrogen atmosphere. The stereochemistry mechanism of the alkoxidation of HSPs was proposed by the 31P NMR tracing experiment. The reaction proceeded via the chlorinated spirophosphorane intermediate with stereoretention of the configuration at phosphorus, followed by the rear and front attack of alkoxide anions to produce alkoxy spirophosphoranes. The reaction mechanism well explained the results of the reaction of HSPs with sodium alcoholates.

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“…Our group has reported that phosphorus− carbon coupling constant 3 J CCNP is sensitive to relative phosphorus configuration. 35,36 The 3 J CCNP of Λ P configuration is larger than that of Δ P configuration for phenoxy spirophosphorane. Generally, the 3 J CCNP value of Δ P configuration is about 3−4 Hz, while it is about 6−8 Hz for Λ P configuration.…”

Section: ■ Introductionmentioning

confidence: 92%

Investigation of the Stereochemical Mechanism of the Nucleophilic Substitution Reaction at Pentacoordinate Phosphorus of Spirophosphorane

et al. 2021

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The stereochemical mechanism of the nucleophilic substitution reaction at pentacoordinate phosphorus (P–V) atom is rarely studied. Here, we report the Atherton-Todd-type reaction of pentacoordinate hydrospirophosphorane with phenolic compounds in detail. The stereochemical mechanism of nucleophilic substitution at P–V atom was proposed by 31P NMR tracing experiment, X-ray diffraction analysis, and density functional theory calculations. The first step of the Atherton-Todd-type reaction is the formation of halogenated spirophosphorane intermediate with retention of configuration at phosphorus definitely. The second step is a nucleophilic substitution reaction at P–V atom of halogenated spirophosphorane. When using CCl4 as a halogenating agent, the reaction of chlorinated spirophosphorane proceeds via SN2(P–V) mechanism, and the backside attack of P–Cl bond is the main pathway. For chlorinated spirophosphorane with ΔP configuration, the completely P-inverted product is normally obtained. As for chlorinated spirophosphorane with ΛP configuration, which has larger steric hindrance behind P–Cl bond, the proportion of P-retained products apparently increases and a pair of diastereoisomers is acquired. Furthermore, if CBr4 is used as a halogenating agent, the nucleophilic substitution reaction of brominated spirophosphorane may go through a SN1(P–V) mechanism to afford a pair of diastereoisomers.

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The ³J_CCNP Coupling Constants of Pentacoordinate Spirophosphorane Derivatives: As a Method to Assign Relative Configuration

Cited by 8 publications

References 15 publications

Investigation of the Asymmetric Addition Reactions Induced by Pentacoordinated Hydrospirophosphorane Substrate

Investigation of the Asymmetric Addition Reactions Induced by Pentacoordinated Hydrospirophosphorane Substrate

Synthesis and Characterization of Alkoxy Spirophosphoranes Prepared from Hydrospirophosphoranes and Sodium Alcoholates

Investigation of the Stereochemical Mechanism of the Nucleophilic Substitution Reaction at Pentacoordinate Phosphorus of Spirophosphorane

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