Diphenyl rhodium chloride

The reaction of bis-phenylpropargyl ether (321) with tris(triphenylphosphine)rhodium chloride in benzene or toluene led to the formation of the unusual organometallic compound (322), which can be viewed as a derivative of an oxygen-rhodium pentalene system. Reaction of the rhodium complex (322) with sulfur leads to the corresponding 4,6-diphenyl-l,3-dihydro[3,4-c]furan (323). The selenium and tellurium analogs (324) and (325) were made in a similar manner (Scheme 111) (76LA1448). 

Tab. 13 Asymmetrische Hydrierung von Acrylsaure-Derivaten mit chiralen Rhodium-Kom-plexen in situ hergestellt aus Bis-[cycloocten]-rhodium(I)-chlorid und 4,5-Bis-[diphenyl-phosphinyl-methyl]-2,2-dimethyl - 1,3-dioxolan (DIOP), eine Auswahl 1 2...

Cuprous chloride tends to form water-soluble complexes with lower olefins and acts as an IPTC catalyst, e.g., in the two-phase hydrolysis of alkyl chlorides to alcohols with sodium carboxylate solution [10,151] and in the Prins reactions between 1-alkenes and aqueous formaldehyde in the presence of HCl to form 1,3-glycols [10]. Similarly, water-soluble rhodium-based catalysts (4-diphenylphosphinobenzoic acid and tri-Cs-io-alkylmethylam-monium chlorides) were used as IPTC catalysts for the hydroformylation of hexene, dodecene, and hexadecene to produce aldehydes for the fine chemicals market [152]. Palladium diphenyl(potassium sulfonatobenzyl)phosphine and its oxide complexes catalyzed the IPTC dehalogenation reactions of allyl and benzyl halides [153]. Allylic substrates such as cinnamyl ethyl carbonate and nucleophiles such as ethyl acetoactate and acetyl acetone catalyzed by a water-soluble bis(dibenzylideneacetone)palladium or palladium complex of sulfonated triphenylphosphine gave regio- and stereo-specific alkylation products in quantitative yields [154]. Ito et al. used a self-assembled nanocage as an IPTC catalyst for the Wacker oxidation of styrene catalyzed by (en)Pd(N03) [155]. 

In another penem building block synthesis, a functionalised azetidinone is reacted with benzyl 2-bromopropionate in the presence of diethylaluminium chloride in hexane/THF. A mixture of epimers is obtained, which has to be separated chromatographically. Afterwards, the lactam nitrogen is protected, and the benzyl residue reductively cleaved. The next steps bear a close resemblance to those of the thienamycin synthesis construction of a jS-ketoester, diazo transfer and rhodium-catalysed insertion of a carbenoid into the lactam N-H bond. Finally, the jS-keto-ester is activated with diphenyl chlorophos-phonate. [60]... 

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