The Reaction of Triphenylphosphine Oxide with Alkyllithium and Grignard Reagents

Seyferth, Dietmar; Welch, Dean E.; Heeren, James K.

doi:10.1021/ja01060a027

Cited by 51 publications

(19 citation statements)

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“…Compounds with four substituents (35; R2-' = alkyl, aryl) cannot be made by these routes. In each group of allyl amines, control over the geometry of the double bond is possible for most compounds, though the synthesis of compounds 2- (32) can be achieved in only low material conversion. 6 432(3) 6 416(3) 5 875(4) 7 038( 1) 6 462(2) 7 496(3) 7 827(3) 8 148(4 82( 1) 577(3) -1 278(4) -2 194(4) -3 096( 5) -3 041( 6) -2 129( 7) -1 229 (5) 679( 4) 1718 (5) 2 330 (7) 1 936 ( 10) 931( 8) 276( 5 2 380(3) -3 535(4) -155(1) 427( 3) 636( 4) 212( 5) 886( 6) 1981( 7) 2 402( 6) 1743( 4) -307( 4) 143( 5) 62( 6) -489 (9) -908(8) -842( 5 Data collection.…”

Section: Nhcophmentioning

confidence: 99%

Horner-Wittig reactions of β-aminoalkyl- and β-N-acylaminoalkyldiphenylphosphine oxides: synthesis of N-allyl amines and amides and 5-diphenylphosphinoyl-2-phenyl-5,6-dihydro-4H-1,3-oxazines

Cavalla¹,

Cruse²,

Warren³

1987

J. Chem. Soc., Perkin Trans. 1

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Section: Nhcophmentioning

confidence: 99%

Horner-Wittig reactions of β-aminoalkyl- and β-N-acylaminoalkyldiphenylphosphine oxides: synthesis of N-allyl amines and amides and 5-diphenylphosphinoyl-2-phenyl-5,6-dihydro-4H-1,3-oxazines

Cavalla¹,

Cruse²,

Warren³

1987

J. Chem. Soc., Perkin Trans. 1

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“…Synthesis of phosphinates from phosphinyl chlorides often produces equal or nearly equal mixtures of diastereomers from which neither diastereomer can readily be obtained in pure form. Organolithium reagents are more reactive but epimerization at phosphorus may occur (94,121,181,197). Many chiral phosphinates are potentially available from 9 via reaction (4).…”

Section: Phosphinate Ester Methodsmentioning

confidence: 99%

Preparation of the Enantiomers of Compounds Containing Chiral Phosphorus Centers

Valentine

1984

Asymmetric Synthesis

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“…To a solution of 300 mg of cyclooctatetraenyldiphenylphosphine (1.04 mmol) in 25 mL of CHClg at 0 °C contained in a three-neck, 100-mL round-bottom flask equipped with an addition funnel, condenser, stopper, and magnetic stirrer was added 10 mL of 30% HgOg in drops from the addition funnel during 0.5 h. The temperature was then raised to ambient for 0.5 h. Water (30 mL) and CHClg (50 mL) were added, the layers were separated, and the organic layer was washed successively with 30 mL of 1 N NaHSOg, HgO, and brine and dried over MgS04. Filtration and removal of solvent gave 321 mg of yellow solid, mp 141.5-143.5 °C, which was recrystallized from cyclohexane (Norit, hot filtration) and dried overnight in an Abderhalden apparatus (78 °C, 0.02 mm) to give 267 mg (84%) of a light vellow solid: mp 142.5-144.0 °C; NMR (CDClg) 7.57 (m, 10.29 H), 6.63 (d, 0.84 H, JPH = 20 Hz), 5.92 (s, 5.74 H); IR (KBr) 3052 (w), 3010 (w), 2966 (w), 2928 (w), 1630 (w), 1616 (w), 1590 (w), 1480 (w), 1440 (m), 1370 (m), 1320 (m), 1277 (w), 1260 (w), 1200 (m), 1177 (s), 1113 (s), 1100 (s). 1070 (w), 1058 (w), 998 (w), 931 (w), 887 (m), 811 (m), 780 (w), 762 (m), 750 (m), 738 (s), 720 (s), 699 (s), 676 (m), 662 (m), 636 (m), 553 (s), 540 (s), 492 (w), 448 (w) cm-1; mass spectrum (20 V, peaks > 10% intensity), m/e 305 (M+ + 1,18), 304 (M+, 83), 303 (37), 202 (33), 201 (100).…”

Section: Methodsmentioning

confidence: 99%

“…Reactions of P-Phenylphosphahomocubane Oxide (1). It seems likely that for the conjugate base of phosphine oxide 1 to fragment should be more difficult than for the phosphonium salt 2, and indeed when 1 is combined in THF with phenyllithium at ambient temperature and the reaction mixture is quenched 20 ÉP C6H5 11 deuterated water the phosphine oxide is recovered, but containing one deuterium atom (Scheme VI). Thus, the lithiated phosphine oxide 9, unlike the ylide 3, is stable in THF at ambient temperature, but that it forms at all in this reaction is remarkable for when the reaction of phosphine oxide 1 in THF with phenyllithium is conducted at -78 °C and quenched with HBr it gives instead the diphenylphosphonium salt 2.10'14 This must mean that at room temperature the oxyphosphorane 8 extrudes phenyllithium and that phenyllithium reacts with 1 quickly at phosphorus but gradually and irreversibly at the a hydrogen.…”

mentioning

confidence: 99%

Preparation and rearrangement of bridgehead phosphorus ylides and their derivatives in the homocubane ring system

Albarella¹,

Katz²

1978

J. Org. Chem.

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Experiments are described in which carbanions are generated at the bridgheads adjacent to phosphorus in phosphonium salt 2 and in phosphine oxide 1. These experiments were undertaken to find ways to make the intermediates in a proposed scheme (Scheme 111) for the synthesis of derivatives of cubane. When attempts are made to prepare the conjugate base of 2 using sodium hexamethyldisilylamide in tetrahydrofuran (THF), the ylide apparently rearranges rapidly to a syn-tricyclooctadienyldiphenylphosphine ( 5 ) , a novel example of the electrocyclic process summarized as eq 5 . The conversion conatitutes a preparation of the tricyclooctadienyl ring system. On oxidation with hydrogen peroxide, 5 gives its phosphine oxide (211, but a t -2 "C this equilibrates with an isomer (22). At 138 "C these isomers rearrange to give 7. Similarly at 74.5 "C, 5 isomerizes to cyclooctatetraenyldiphenylphosphine (6), but shows no evidence of giving an isomer analogous to 22. Unlike the carbanion 3 derived from 2, lithiated phosphine oxide 1 is stable in solution at ambiient temperature. This lithium derivative can be made from 1 and phenyllithium in THF at room temperature, while at -78 "C the same reagents give 8. D20, CH31, and ( C G H~S )~ react with the lithiated material to introduce substituents adjacent to phosphorus. The thiophenyl substituent can be oxidized to the sulfone (16), and this with sodium hexamethyldisilylamide gives 18. With phenyllithium 16 gives the analogue 20. These last rearrangements are novel, and since 1 does not undergo them, they reflect the leaving ability of sulfone anions The cubic hydrocarbon CsHs, known as cubane, was first synthesized by Eaton and Cole in 1964.' Shortly afterwards a related synthesis was reported by Barborek, Watts, and Pettit,2 and additional ways to arrive a t intermediate molecules on the original routes were found by Chin, Cuts, and Masamune3 and by Eaton and Cole.4 These syntheses, and all of those developed since for derivatives of ~u b a n e ,~ employ as a key step the Favorskii rearrangement6 of an a-bromohomocubanone (Scheme I), and despite difficulties experienced in some laboratories,5f,c although not in other^,^^^^ and despite the length of the synthesis, the original route of Eaton and Cole' remains the most effective. Alternative syntheses have not been reported and seem to have been sought only rarely.'The availability of phenylphosphahomocubane oxide from the cyclooctatetraenyl dianion (Scheme II)8-10 suggested that another route to cubane might be found if a phosphorus analogue of the Favorskii rearrangement could be discovered (Scheme 111), and the research described here was toward this goal. A sulfur analogue of such arrangements, the RambergBacklund rearrangement,Il has been applied effectively in many syntheses, but because it proceeds by way of an episulfone and fails when the intermediate three-membered ring is highly strained, path B in Scheme 111 is unlikely. Path A, Br OH ---1 0 ; Scheme I Scheme I1 2 L i C , H , P C I O P C 6 H 5 prm Scheme 111 NU c 1Bp< C...

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The Reaction of Triphenylphosphine Oxide with Alkyllithium and Grignard Reagents

Cited by 51 publications

References 0 publications

Horner-Wittig reactions of β-aminoalkyl- and β-N-acylaminoalkyldiphenylphosphine oxides: synthesis of N-allyl amines and amides and 5-diphenylphosphinoyl-2-phenyl-5,6-dihydro-4H-1,3-oxazines

Horner-Wittig reactions of β-aminoalkyl- and β-N-acylaminoalkyldiphenylphosphine oxides: synthesis of N-allyl amines and amides and 5-diphenylphosphinoyl-2-phenyl-5,6-dihydro-4H-1,3-oxazines

Preparation of the Enantiomers of Compounds Containing Chiral Phosphorus Centers

Preparation and rearrangement of bridgehead phosphorus ylides and their derivatives in the homocubane ring system

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