Reduction triphenylphosphine rhodium chloride

Reduction of the double bond only was achieved by catalytic hydrogenation over palladium prepared by reduction with sodium borohydride. This catalyst does not catalyze hydrogenation of the aldehyde group [31]. Also sodium borohydride-reduced nickel was used for conversion of cinnamaldehyde to hydrocinnamaldehyde [31]. Homogeneous hydrogenation over tris(triphenylphosphine)rhodium chloride gave 60% of hydrocinnamaldehyde and 40% of ethylbenzene [5(5]. Raney nickel, by contrast, catalyzes total reduction to hydrocinnamyl alcohol [4S. Total reduction of both the double... 

Vilsmeier reaction to the chloroaldehyde (106), followed by reductive meth-ylation, yielded the aldehyde 107 (Scheme 14) with the precedented stereochemical outcome. Attempted halogenation of the derived neopentyl-type alcohol was unsuccessful under a variety of conditions, so an alternative scheme involving two successive Wittig-type reactions was developed. The aldehyde 107 was converted to the unsaturated aldehyde 108 by the method of Nagata and Hayase. Reduction with triethylsilane and tris (triphenylphosphine) rhodium chloride was followed by condensation with isopropylidene phosphorane to give the desired product 109. 

Nitrosyltris(triphenylphosphine)rhodium has previously been prepared by sodium-amalgam reduction of a mixture of rhodium nitrosyl chloride and triphenylphosphine in tetrahydrofuran.32 Preparations from hydridotetrakis(triphenylphosphine)rhodium(I) and nitric oxide,24 and from rhodium trichloride, nitric oxide, triphenylphosphine, and zinc dust have also been reported.35 The following synthesis1 is convenient and rapid. 

The second approach to the synthesis of CNT 31 [81] involves opening of the 2, 3 -anhydro-P-D-lyxonucleoside 50 with lithium cyanide to give stereo-selectively 51 (R = Trityl). Attempts to deoxygenate the 2 -OH group by reaction with Ar,AT-thiocarbonyldiimidazole gave the a,P-unsaturated nitrile 48 (R = trityl). Reduction of the double bond of 48 (R = trityl) with triethylsilane and tris(triphenylphosphine)rhodium (I) chloride gave a mixture of the two... 

Meerwin s ester has been used as a starting point for the synthesis of 3,7-disub-stituted bicyclo[3,3,2]decanes. Thus, the homoadamantanedione dicarboxylic acid (677) was prepared by standard methods and converted into (678) by sequential Wolff-Kishner reduction and decarbonylation of the bis-acid chloride with catalytic chlorocarbonylbis(triphenylphosphine)rhodium. Fragmentation of (678) with aqueous alkali gave (679). 

Tris(triphenylphosphine)rhodium(I) chloride is a catalyst for the reaction of triethylsilane with thiophenol [352] and nickel catalyses the reaction of diethyldi-hydrosilane with some alkane thiols [353]. Chlorodihydrophenylsilane reacts with dimethyldisulphide at — 80°C to form chlorobis(methylthio)phenylsilane [354] (77 %). Phenylselenotrimethylsilane [355,356] (b.p. 70°C at 266 Pa = 2 m Hg) can be prepared in excellent yield from phenylselenol or by a reductive silylation of diphenyldisilenide (Scheme 3.13) ... 

Raney nickel, 135, 312,411 Ratcliffe reagent, 37, 70 Redudion decyanization, 324-325 Reductive dimerization, 369 Reformatsky-type reactions, 151-152 Resolution, 79,113 Resorcinol dibenzoate, 57 Retinal, 372 Retroaldol reaction, 303 RhodiumGl) acetate, 76, 313 Rhodium(II) n-butanoate, 313 Rhodium(II) carboxylates, 313 Rhodium(III) chloride, 313-314 Rhodium(III) chloride-Triphenylphosphine, 314... 

The use of ruthenium chloride triphenylphosphine complex on the keto system reduced only the C-1 double bond without further reduction such as can occur with the corresponding rhodium complex Chromium (II) chloride reduces... 

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