A Simple Resolution Procedure Using the Staudinger Reaction for the Preparation of <i>P</i>-Stereogenic Phosphine Oxides

Andersen, Neil G.; Ramsden, Philip; Che, Da‐Qing; Parvez, Masood; Keay, Brian A.

doi:10.1021/jo015909u

Cited by 31 publications

(31 citation statements)

References 51 publications

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“…The 31 P NMR spectra of 3, 4, 5a, and 5b displayed strongly upfield shifted signals (δ 31 P -20 to -32 in CD 3 CN) indicating the strong possibility of P-N transannular bonding. Interestingly, 5a showed a rather solvent dependent 31 C NMR data for compounds 5a and 5b are also consistent with transannulated structures.…”

Section: Reactions Of Proazaphosphatranes With Arysulfonylsupporting

confidence: 66%

“…31 P NMR (CD 3 CN): δ -21.9 (s). 1 H NMR (CD 3 CN): δ 1.17 (d, CH 3 , 3 J(HH) ) 6.72 Hz, 18 H), 2.17 (s, C 6 H 4 CH 3 -4, 3 H), 2.54 (s, C 6 H 2 (CH 3 ) 2 -2,6, 6 H), 2.96 (m, CH 2 N ax , 6 H), 3.09 (m, CH 2 N eq , 6 H), 3.97 (m, CH, 3 H), 6.63 (s, C 6 H 2 , 2 H).…”

Section: Synthesis Of [N(ch 2 Ch 2 N I Pr) 3 Pn 3 ][So 2 C 6 H 2 Me 3mentioning

confidence: 99%

“…Mp 132-133°C. 31 P NMR (CD 3 CN): δ 37.5 (s). 1 H NMR (CD 3 CN): δ 2.29 (s, C 6 H 4 CH 3 -4, 3 H), 2.65 (d, CH 3 , 2 J(PH) ) 8.4 Hz, 18 H), 2.77 (m, CH 2 N ax , 6 H), 2.92 (m, CH 2 N eq , 6 H), 7.25 (m, C 6 H 4 , 4 H).…”

Section: Synthesis Of {[N(ch 2 Ch 2 Nme) 3 P] 2 (µ-N 3 )}[So 2 C 6 H mentioning

confidence: 99%

“…The reaction mixture was stirred for 5 h, and then, acetonitrile was removed under reduced pressure to give 11 as an oil in quantitative yield. 31 P NMR (C 6 D 6 ): δ 42.0 (s). 1 H NMR (CD 3 -CN): δ 2.30 (s, C 6 H 4 CH 3 -4, 3 H), 2.68 (d, CH 3 , 3 J(PH) ) 9.32 Hz, 36 H), 7.26 (m, C 6 H 4 , 4 H).…”

Section: Synthesis Of {[(Me 2 N) 3 P] 2 (µ-N 3 )}[So 2 C 6 H 4 Me-4] mentioning

confidence: 99%

“…Proton-coupled 31 P NMR and 31 P-1 H COSY NMR spectra were utilized to assign unambiguously the peak positions for 10-12. 31 P NMR (CD 3 CN): δ 25.8, 38.7, and 42.5 (singlets for 10, 12, and 11, respectively). 1 H NMR (CD 3 CN): δ 2.37 (s, C 6 H 4 CH 3 -4, 9 H, 10, 11 and 12), 2.56 (d, CH 3 , 3 J(PH) ) 9.32 Hz, 18 H, 10), 2.69 (d, CH 3 , 3 J(PH) ) 9.30 Hz, 36 H, 11), 2.78 (d, CH 3 , 3 J(PH) ) 11.00 Hz, 18 H, 12), 7.32 (m, C 6 H 4 , 12 H, 10, 11, 12).…”

Section: Synthesis Of {[(Me 2 N) 3 P] 2 (µ-N 3 )}[So 2 C 6 H 4 Me-4] mentioning

confidence: 99%

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Reactions of Tris(amino)phosphines with Arylsulfonyl Azides: Product Dependency on Tris(amino)phosphine Structure

2002

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The Staudinger reaction of N(CH2CH2NR)3P [R = Me (1), Pr (2)] with 1 equiv of N3SO2C6H4Me-4 gave the ionic phosphazides [N(CH2CH2NR)3PN][SO2C6H4Me-4] [R = Me (3), R = Pr (5a)], and the same reaction of 2 with N3SO2C6H2Me3-2,4,6 gave the corresponding aryl sulfinite 5b. On the other hand, the reaction of 1 with 0.5 equiv of N3SO2Ar (Ar = C6H4Me-4) furnished the novel ionic phosphazide [[N(CH2CH2NMe)3P]2(mu-N3)][SO2Ar] (6). Data that shed light on the mechanistic pathway leading to 3 were obtained by low temperature 31P NMR spectroscopy. A crystal and molecular structure analysis of the phosphazide sulfonate [N(CH2CH2NMe)3PN3][SO3C6H4Me-4] (4), obtained by atmospheric oxidation of 3, indicated an ionic structure, the cationic part of which is stabilized by a transannular P-N bond. A crystal and molecular structure analysis of 6 also indicated an ionic structure in which the cation features two untransannulated N(CH2CH2NMe)3P cages bridged by an azido group in an eta 1: mu: eta 1 fashion. The reaction of P(NMe2)3 with N3SO2Ar (Ar = C6H4Me-4) in a 1:0.5 molar ratio furnished [[(Me2N)3P]2(mu-N3)][SO2-Ar] (11) in quantitative yield. On the other hand, the same reaction involving a 1:1 molar ratio of P(NMe2)3 and N3SO2Ar produced a mixture of 11, [(Me2N)3PN3][SO2Ar] (12), and the iminophosphorane (Me2N)3P=NSO2Ar (10). In contrast, the bicyclic tris(amino)phosphines MeC(CH2NMe)3P (7) and O=P(CH2NMe)3P (8) reacted with N3SO2-Ar (Ar = C6H4Me-4) to give the iminophosphorane MeC(CH2NMe)3P=NSO2Ar (14) (structured by X-ray means) and O=P(CH2NMe)3P=NSO2Ar (16) via the intermediate phosphazides MeC(CH2NMe)3PN3SO2Ar (13) and O=P(CH2NMe)3PN3SO2Ar (15), respectively. The variety of products obtained from the reactions of arylsulfonyl azides with proazaphosphatranes (1 and 2), acyclic P(NMe2)3, bicyclic tris(amino)phosphines 7 and 8 are rationalized in terms of steric and basicity variations among the phosphorus reagents.

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Section: Reactions Of Proazaphosphatranes With Arysulfonylsupporting

confidence: 66%

Section: Synthesis Of [N(ch 2 Ch 2 N I Pr) 3 Pn 3 ][So 2 C 6 H 2 Me 3mentioning

confidence: 99%

Section: Synthesis Of {[N(ch 2 Ch 2 Nme) 3 P] 2 (µ-N 3 )}[So 2 C 6 H mentioning

confidence: 99%

Section: Synthesis Of {[(Me 2 N) 3 P] 2 (µ-N 3 )}[So 2 C 6 H 4 Me-4] mentioning

confidence: 99%

Section: Synthesis Of {[(Me 2 N) 3 P] 2 (µ-N 3 )}[So 2 C 6 H 4 Me-4] mentioning

confidence: 99%

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Reactions of Tris(amino)phosphines with Arylsulfonyl Azides: Product Dependency on Tris(amino)phosphine Structure

2002

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Staudinger Reaction

2010

Comprehensive Organic Name Reactions and Reagents

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The reaction between an azide and triphenylphosphine (or phosphonite) to produce an iminophosphorane (the nucleophilic aza ‐ylide) and subsequent hydrolysis to yield a primary amine is generally known as the Staudinger reaction. This reaction is a specific, high‐yielding reaction in which the iminophosphorane intermediate hydrolyzes spontaneously in the presence of water. The most important modification of Staudinger reaction is probably its extension to the formation of peptide bonds, employing the high nucleophilicity of nitrogen atom in aza y‐lide in the presence of an ester group. This reaction has been applied in organic synthesis, especially in the preparation of peptide bonds in a living system.

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Organische Azide – explodierende Vielfalt bei einer einzigartigen Substanzklasse

et al. 2005

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Seit der Entdeckung der organischen Azide vor über einhundertvierzig Jahren durch Peter Grieß wurde eine Reihe von Synthesen für diese energiereichen Moleküle entwickelt. In letzter Zeit haben sich völlig neue Perspektiven durch Anwendungen in der Peptidchemie, der kombinatorischen Chemie und der Heterocyclensynthese ergeben. Auf dem interdisziplinären Gebiet zwischen Chemie, Biologie, Medizin und Materialwissenschaften nehmen organische Azide inzwischen einen wichtigen Raum ein. In diesem Aufsatz werden die Grundzüge der Azid‐Chemie dargelegt und aktuelle Entwicklungen auf diesem Gebiet beleuchtet. Der Schwerpunkt liegt dabei auf Cycloadditionen (Huisgen‐Reaktion), Aza‐Ylidchemie und der Synthese von Heterocyclen. Weitere Reaktionen wie die Aza‐Wittig‐Reaktion, Sundberg‐Umlagerung, Staudinger‐Ligation, Boyer‐ und Boyer‐Aubé‐Umlagerung, Curtius‐Umlagerung, Schmidt‐Umlagerung sowie die Hemetsberger‐Umlagerung zeugen von der Vielfältigkeit moderner Azid‐Chemie.

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A Simple Resolution Procedure Using the Staudinger Reaction for the Preparation of P-Stereogenic Phosphine Oxides

Cited by 31 publications

References 51 publications

Reactions of Tris(amino)phosphines with Arylsulfonyl Azides: Product Dependency on Tris(amino)phosphine Structure

Reactions of Tris(amino)phosphines with Arylsulfonyl Azides: Product Dependency on Tris(amino)phosphine Structure

Staudinger Reaction

Organische Azide – explodierende Vielfalt bei einer einzigartigen Substanzklasse

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