Stereo- and regiospecific ligand substitution reactions of mono- and dinuclear rhodium(III) phosphine complexes

Cotton, F. Albert; Eglin, Judith L.; Kang, Seong Joo

doi:10.1021/ja00036a082

Cited by 11 publications

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Effects of Halides and Related Ligands on Reactions of Carbonylruthenium Complexes (Ru0–RuII)

Lavigne¹

1999

Eur. J. Inorg. Chem.

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While the primary motivation of fundamental studies on carbonylhalotriruthenium complexes was to understand the promoter effect of halides on certain ruthenium‐based catalytic systems of industrial relevance, such complexes have gained significance in their own right due to their remarkable ability to provide low‐activation energy pathways for the coordination of organic substrates. Limitations inherent to the fragility of these prototypes led to the design and development of a related family of more sophisticated derivatives where an aminopyridyl group serves as an alternate hemilabile ancillary ligand. Studies of their reactivity have revealed the possibility of achieving a number of stoichiometric or moderately catalytic “cluster‐mediated” transformations of organic substrates under very mild conditions. Yet, the viability of these systems is still limited to a narrow low‐energy domain. By contrast, halotriruthenium derivatives are still seen to function as catalyst precursors under the actual conditions of certain catalytic reactions where they act as sources of ruthenium(II) halide complexes that become the active components of the system. The second part of the review focuses on novel aspects of their fascinating chemistry.

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Effects of Halides and Related Ligands on Reactions of Carbonylruthenium Complexes (Ru0–RuII)

Lavigne¹

1999

Eur. J. Inorg. Chem.

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Bildung von Alkyl(dicarbonyl)(chloro)ruthenium‐Dimeren bei der Ru‐katalysierten Addition von Alkylformiaten an Ethen

1997

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ZUSCHRIFTENMo,,-Strahlung (i = 0.71071 A), T = 298 K, 0-20-Scan, 5121 gemessene Reflexe, davon 4977 unabhingige (R?", = 0.0407), die alle in der Verfeinerung verwendet wurden. Lorentz-und Polarisationskorrektur, p = 2.60 mm-I [ A / u],,, = 0.321, 419 verfeinerte Parameter, R1 = 0.0409 (fur 3762 Reflexe mit />2u(/)), wR2 = 0.1000 (gegen lF21). Max./min. Restelektronendichte in der letzten Differenzkarte 0.854; -0.374 e k 3 . 4: C,,H,,Cu,,N,,036, 0.3 x 0.4 x 0.6 mm3, monoklin, Raumgruppe /2/a, a = 27.653(3), b = 16.366(2), c = 29.058(3) A, fl = 110.37(1)", V = 12328(2) A3, Z = 4, pbrr = 1.462 gcm-3, 20,,. = 50'. Mo,,-Strahlung (% = 0.71073 A), T = 298 K, 0-20-Scan, 11 124 gemessene Reflexe, davon 10851 unabhingige (Rin, = 0.0215), die alle in der Verfeinerung verwendet wurden. Lorentz-, Polarisations-und Y-Scan-Korrektnr, I( = 2.099 mm-', [A/u],,, = 0.436, 781 verfeinerte Parameter, Rl = 0.0483 (fur 7559 Retlexe mit 1>2u(I)), nR2 = 0.1408 (gegen IF21. Max./min. Restelektronendichte in der letzten Differenzkarte 1.936/ -0.364 e k ' . Die

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Generation of Alkyl(dicarbonyl)(chloro)‐ruthenium Dimers in the Ruthenium‐Catalyzed Addition of Alkyl Formates to Ethylene

Fabre

Kalck

Lavigne³

1997

Angew. Chem. Int. Ed. Engl.

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COMMUNICATIONS treated with 2.2 equivalents of 4 (prepared from l-triisopropyl-siIylo~y-3,3-diiodopropane~~~~ and Et,Zn) and 1 equivalent of 3 (Scheme 3). Furthermore, the diastereo-and enantioselectivity for these processes were excellent. [20] In summary, we have developed an expedient and efficient synthesis of enantiomerically enriched 1,2,3-substituted cyclopropanes from allylic alcohols. In addition, we have presented the first cyclopropanation reaction of a functionalized iodoalkylzinc reagent. Applications of this methodology to natural product synthesis is currently underway. Experimental SectionTo a solution of Et,Zn (113 pL, 1.1 mmol) in CH,CI, (5 mL) at 0°C was added CH,CHI, (222 pL, 2.2 mmol) over 5 min. After 10 min of stirring at 0 "C, a solution of the allylic alcohol (0.5 mmol) and (R,R)-dioxaborolane (3) (149 mg, 0.55 mmol) in CH,CI, (2 mL) was added rapidly by cannula. The ice bath was removed, and the reaction was stirred until TLC analysis showed complete consumption of the starting material (1 h). The reaction mixture was then poured into saturated aqueous NH,CI (20mL). and 10% aqueous HCI (10mL) was added. The mixture was extracted three times with ether (10mL). and the combined organic layers were stirred vigorously with 5hl aqueous KOH (15 mL) for 12 h, washed with saturated aqueous Na,SO, (15 mL). with saturated aqueous NH,CI (15 mL), and with saturated aqueous NaCl(15 mL). dried over MgSO,, and concentrated under reduced pressure. The residue was purified by flash chromatography to afford the desired cyclopropane.

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Stereo- and regiospecific ligand substitution reactions of mono- and dinuclear rhodium(III) phosphine complexes

Cited by 11 publications

References 0 publications

Effects of Halides and Related Ligands on Reactions of Carbonylruthenium Complexes (Ru0–RuII)

Effects of Halides and Related Ligands on Reactions of Carbonylruthenium Complexes (Ru0–RuII)

Bildung von Alkyl(dicarbonyl)(chloro)ruthenium‐Dimeren bei der Ru‐katalysierten Addition von Alkylformiaten an Ethen

Generation of Alkyl(dicarbonyl)(chloro)‐ruthenium Dimers in the Ruthenium‐Catalyzed Addition of Alkyl Formates to Ethylene

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