Stable cycloalkyl pentavalent phosphoranes

Katz, Thomas J.; Turnblom, E. Wayne

doi:10.1021/ja00725a087

Cited by 18 publications

(18 citation statements)

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“…The solution was cooled to 0 "C. whereupon a solution of 270 mg of 85% m-chloroperbenzoic acid (1.34 mmol, 6.82 equiv) in 15 mL of CHCl:, was added in drops from the addition funnel during 0.5 h. The reaction mixture was stirred for 0.5 h a t 0 "C and then at ambient temperature for 3.0 h. Chloroform (50 mL) was added, and the solution was washed successively with 30 mL of 1 N NaHSO.3, HeO, and brine and dried over MgS04. Removing the solvent gave 128 mg of a white solid, which after recrystallization from mel.hano1 produced 57 mg (57% yield) of a white powder: mp 300-301 "C; lH NMR (MenSO-ds) 6 7.60 (m, 15.20 H), 4.30 (m, 3.42 (141,367 (27), 253 (39), 242 (15), 179 (14), 178 (19), 165 ( l l ) , 164 (20), 149 (111,147 (161,146 (20),126 (101,125 (100),119 (IO), 118 (14),109 (10). phenylphosphinic Acid (19).…”

Section: P-phenyl-anda'-bis( Benzenesulfony1)phosphahomocubanementioning

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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Section: P-phenyl-anda'-bis( Benzenesulfony1)phosphahomocubanementioning

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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“…The direct irradiation of 1 (Pyrex filter, THF solvent, 6 hr, room temperature) provided dimers A and B in 56 and 25% yields, respectively.2 Both A and B were Gibbons, N. Nakatsuka, and S. Masamune, J. Amer. Chem.…”

Section: Sirmentioning

confidence: 99%

“…d By glpc analysis. 6 Trimethylamine-monoalkylborane derivative. 1 Pyridine-monoalkyIborane derivative.…”

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confidence: 99%

Geometry of the anti-tricyclo[3.1.0.02,4]hexane and cyclohexa-1,4-diene systems

Masamune¹,

Bennett²,

Purdham³

et al. 1971

J. Am. Chem. Soc.

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“…A similar ligand coupling within an intermediary u-phosphorane is expected to be possible. Indeed, many examples probably belong to this type of reaction [1, [7][8][9][10][11]:…”

Section: Introductionmentioning

confidence: 99%

Reactions of 2‐Pyridyl Substituted Phosphine Oxides and Phosphonium Salts with Organometallic Reagents and in Aqueous Media

Uchida

Onoue

Tada

et al. 1990

Heteroatom Chemistry

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Phosphine oxides bearing two or three 2‐pyridyl groups react with organometallic reagents affording 2,2′‐bipyridyl, 2‐substituted pyridines and pyridine in good yields. Phosphonium salts and phosphine oxides, bearing at least two 2‐pyridyl or substituted 2‐pyridyl groups also give the corresponding 2,2′‐bipyridyls and pyridines upon treatment with acid or neutral solvents such as water and alcohols in substantial yields. The 2,2′‐bipyridyls are considered to be formed by ligand coupling within the pentacoordinated phosphorus intermediate formed incipiently during the reaction.

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Stable cycloalkyl pentavalent phosphoranes

Cited by 18 publications

References 0 publications

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

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

Geometry of the anti-tricyclo[3.1.0.02,4]hexane and cyclohexa-1,4-diene systems

Reactions of 2‐Pyridyl Substituted Phosphine Oxides and Phosphonium Salts with Organometallic Reagents and in Aqueous Media

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