2.6- diphenyl-4- 3- propenyl

P-Menthylphosphetanes 77, in which an optical active dioxolane group is introduced at the a-position, have also provided asymmetric catalytic activity in the palladium-catalyzed allylic nucleophilic substitution of 1,3-diphenyl-propenyl acetate with the sodium salt of dimethyl malonate (Equation 12). 

The photochemical behaviour of 2-aryl-l,3-diphenyl propenyl anions has been reported. " ... 

Hence, for e.vo/e propenyl)lithium in THF a free energy of activation of AG 38, c of 17 keal/mol was found, with a half-life period of 8 minutes at this temperature17. 

Finally, 2-allyl-4,5-tra ,s-diphenyl-l,3-bis(4-methylphenylsulfonyl)-l,3,2-diazaborolidincs have been used74. The 2-propenyl derivative undergoes highly stereoselective reactions with achiral aldehydes (95 - 97% ee) the ( )-2-butenyl derivatives (91-95% ee) and the analogous 2-chloro- and 2-bromo-2-propenyl derivatives (84-99% ee) also give excellent results in reactions with achiral aldehydes. 

Results of the asymmetric 2-propenylborations of several chiral a- and /i-alkoxy aldehydes are presented in Table 11 74a-82 84. These data show that diisopinocampheyl(2-propenyl)borane A and l,3-bis(4-methylphenylsulfonyl)-4,5-diphenyl-2-propenyl-l,3,2-diazaborolidine C exhibit excellent diastereoselectivity in reactions with chiral aldehydes. These results are in complete agreement with the enantioselectivity of these reagents in reactions with achiral aldehydes (Section 1.3.3.3.3.1.4.). In contrast, however, the enantioselectivity of reactions of the tartrate 2-propenylboronate B (and to a lesser extent the tartrate (/i)-2-butenylhoronate)53b is highly... 

Chiral phosphinous amides have been found to act as catalysts in enantio-selective allylic alkylation. Horoi has reported that the palladium-catalyzed reaction of ( )-l,3-diphenyl-2-propenyl acetate with the sodium enolate of dimethyl malonate in the presence of [PdCl(7i-allyl)]2 and the chiral ligands 45 gave 46 in 51-94% yields and up to 97% ee (Scheme 38). It is notorious that when the reaction is carried out with the chiral phosphinous amide (S)-45a, the product is also of (S) configuration, whereas by using (R)-45b the enantiomeric (R) product is obtained [165]. 

Diamine 108 led to 95% ee for the alkylation of l,3-diphenyl-2-propenyl acetate with 90% yield. By polycondensation with a diacid chloride or polyaddition with a diisocyanate, this ligand led, respectively, to an insoluble poly(amide) 109 or poly(urea) 110 with excellent yields. Poly(amide) 109 gave a better ee (80%) than poly(urea) 110 (38%), albeit with a lower conversion (respectively, 38 and 72%), when they were used as palladium hgands... 

Catalytic reaction conditions [Pd/l]j.oii (ca. 2.35 x 10 mmols) and 1 (5.8 X 10 mmols) was dissolved in 2cm of CH2CI2. roc-1,3-diphenyl-2-propenyl acetate (252mg, 1 mmol), dissolved in 7 cm of CH2CI2, was added, followed by dimethyl malonate (396mg, 3mmols), BSA (610mg, 3 mmols), and a catalytic amoimt of KOAc. After each 24 h, 1 mmol of roc-I was added. 

Sulfoximines bearing a chiral sulfur atom have recently emerged as valuable ligands for metal-catalysed asymmetric synthesis.In particular, C2-symmetric bis(sulfoximines), such as those depicted in Scheme 1.51, were applied to the test reaction, achieving enantioselectivities of up to 93% ee. The most selective ligand (R = c-Pent, R = Ph) of the series was also applied to the nucleophilic substitution reaction of l,3-diphenyl-2-propenyl acetate with substituted malonates, such as acetamido-derived diethylmalonate, which provided the corresponding product in 89% yield and 98% ee. 

Scheme (17) illustrates the synthesis of the diphenyl ester (118) of (l-amino-2-propenyl)phosphonic acid (119), an... 

Treatment of the (—)-menthone-derived 2/7-1,3-benzoxazin-4(3//)-one 202 with triflic anhydride gave the triflate 203 in quantitative yield. Palladium-catalyzed cross-coupling of 203 with 2-pyridylzinc halide resulted in formation of an approximately 3 1 mixture of the 4-(2-pyridyl)-2//-l,3-benzoxazine 204 and a 4-imino-l,3-benzodioxane derivative 205 (Scheme 36). Compound 205 was formed by the isomerization of 203, which occurred with complete retention of stereochemistry. The 4-(2-pyridyl)-l,3-benzoxazine derivative 204 was applied in enantioselective allylic alkylations of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate as a chiral ligand inducing a 62% ee in the product <2005JOM(690)2027>. 

As described in the previous section, when acyclic and symmetric allylic esters such as l,3-diphenyl-2-propenyl acetate and l,3-dialkyl-2-propenyl esters are used as substrates, high to excellent enantioselective allylic alkylation is performed by using a variety of chiral ligands. In contrast, the number of successful examples of the asymmetric allylic alkylation of acyclic and unsymmetric allylic esters is relatively limited. 

When l,l-dimethoxy-4-propyl-2,6-diphenyl-A5-phosphorin (53) is transformed into its 4-carbenium tetrafluoroborate (54) and treated with a base the 4-(l-propenyl) derivative (55) is formed. This, by a two phase oxidation with KMn04, gives the aldehyde (56) which can be further transformed, e.g. into the nitrile (57 equation 34) (75AG(E)lll). An Arbusov type dealkylation of the cation salts (49) (or 54) with LiBr gives the phosphinic ester (58 equation (35)). 

To a solution of 250 mg of the 4b-methyl-ip-(2-formylmethyl)-2p-formyl-2-(3,3,3-hydroxydiphenylpropyl)-4p,7a-dihydroxyperhydrophenanthrene ip-methyl acetal 2p,4p-lactol methyl ether 7a-acetate in 10 ml of benzene and 1.0 ml of pyridine at 0°C was added 0.5 ml of thyonyl chloride. After standing at 0°C for 15 min, the solution was poured onto iced sodium bicarbonate, and resulting mixture was extracted with ether. The extract was dried over magnesium sulfate, and the ether was removed under reduced pressure. Pyridine (20 ml) was added and solution was heated at 100°C for 20 min. The solution was then concentrated to dryness under reduced pressure and the residue was dissolved in a small volume of benzene. The benzene solution was poured on 6 g of florisil elution with ether provided 230 mg of colorless 4b-methyl-ip-(2-formylmethyl)-2p-formyl-2-(3,3-diphenyl-2-propenyl)-4p,7a-dihydroxyperhydrophenanthrene ip-methyl acetal 2p,4p-lactol methyl ether 7a-acetate. 

Recently, Majoral et al. described the synthesis of a third-generation phosphorus-containing dendrimer possessing 24 chiral iminophosphine end groups derived from (2S)-2-amino-l-(diphenylphosphinyl)-3-methylbutane (Fig. 11) [32]. The dendritic catalyst was tested in allylic substitution reactions, using rac-(.E)-diphenyl-2-propenyl acetate or pivalate as substrates. The observed enantioselectivities were good to excellent (max. 95% ee) in all reactions. After completion of the catalytic reaction, the catalyst could be reused at least twice after precipitation and filtration. A slight decrease... 

Further information on the mechanisms of these addition reactions is found in a study of the reaction of "phenylpalladium acetate with trans- and cfs-propenylbenzene 24>. The trans-isomer reacted in nearly quantitative yield at 30 °C in methanol solution to produce trans-1,2-diphenyl-l-propene. About a half of a percent yield of l,2-diphenyl-2-propene was also found. Only a trace of the Markovnikov product 1,1-diphenyl-l-propene was seen (See Chart 1). The reaction of cfs-propenyl-benzene under the same conditions produced an 85% yield of olefins containing 65% of cis- 1,2-diphenyl- 1-propene, 22% trans-1,2-diphenyl-1 -propene, 10% 2,3-diphenyl-l-propene and about 3% of 1,1-diphenyl-1-propene. The major products in both reactions are the one expected from a cis-anti-Markovnikov addition of the phenylpalladium acetate followed by a cis-elimination of "hydrodopalladium acetate . There is practically no Markovnikov addition. 

Auch cyclische Phosphinsaure-ester lassen sich mit Grignard-Verbindungen umsetzen. So entsteht aus 2,5-Diphenyl-3-methyl-2,5-dihydro-l,2-oxaphosphol-2-oxid mit Phenyl-magnesiumbromid Diphenyl- (3-hydroxy-1 -methyl-3-phenyl-l-propenyl)-phosphan-oxid (Schmp. 154-156°) zu 77%2 6 ... 

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