51482-36-1

Upstream product

• 3485-84-5 N-vinylphthalimide 
• 201230-82-2 carbon monoxide 
• 2453-90-9 N-(3,3-diethoxypropyl)phthalimide 
• 70058-19-4 2-((2S)-1-hydroxypropan-2-yl)-1H-isoindole-1,3(2H)-dione 
• 85-44-9 phthalic anhydride 
• 4192-28-3 Phth-L-Ala-OH 
• 4306-25-6 (S)-2-phthalimidopropionyl chloride 

Downstream Products

• 676558-59-1 2-{(S)-2-[(E)-Benzylimino]-1-methyl-ethyl}-isoindole-1,3-dione 

Relevant academic research and scientific papers

Effector enhanced enantioselective hydroformylation

In this communication, we report rhodium DIMPhos complexes with an integrated DIM-receptor that can bind carboxylate containing effectors and their application in the rhodium catalyzed hydroformylation reaction. The binding of chiral effectors in non-chiral [Rh(DIMPhos)] catalysts does not lead to enantioselective hydroformylation, but the binding of either achiral or chiral effectors can significantly enhance the enantioselectivity induced by the chiral Rh-metal complexes. For example, the supramolecular complex [Rh]/[1S?L3] displays high regio- and enantioselectivity in the hydroformylation of vinyl acetate (72% ee, and b/l >99), whereas in absence of this effector the ee is around 17%.

KetoABNO/NOx Cocatalytic Aerobic Oxidation of Aldehydes to Carboxylic Acids and Access to α-Chiral Carboxylic Acids via Sequential Asymmetric Hydroformylation/Oxidation

A method for aerobic oxidation of aldehydes to carboxylic acids has been developed using organic nitroxyl and NOx cocatalysts. KetoABNO (9-azabicyclo[3.3.1]nonan-3-one N-oxyl) and NaNO2 were identified as the optimal nitroxyl and NOx sources, respectively. The mildness of the reaction conditions enables sequential asymmetric hydroformylation of alkenes/aerobic aldehyde oxidation to access α-chiral carboxylic acids without racemization. The scope, utility, and limitations of the oxidation method are further evaluated with a series of achiral aldehydes bearing diverse functional groups.

Iterative asymmetric hydroformylation/Wittig olefination sequence

Over and over again: Various alkenes underwent the title reaction in the presence of rhodium/bis(diazaphospholane) complexes to give γ-chiral α,β-unsaturated carbonyl products (46-96 % yield) with high enantioselectivity (90-99 % ee). Iterative sequences

Enantioselective hydroformylation of N-vinyl carboxamides, allyl carbamates, and allyl ethers using chiral diazaphospholane ligands

Rhodium complexes of diazaphospholane ligands catalyze the asymmetric hydroformylation of N-vinyl carboxamides, allyl ethers, and allyl carbamates; products include 1,2- and 1,3-aminoaldehydes and 1,3-alkoxyaldehydes. Using glass pressure bottles, short reaction times (generally less than 6 h), and low catalyst loading (commonly 0.5 mol %), 20 substrates are successfully converted to chiral aldehydes with useful regioselectivity and high enantioselectivity (up to 99% ee). Chiral Roche aldehyde is obtained with 97% ee from the hydroformylation of allyl silyl ethers. Commonly difficult substrates such as 1,1- and 1,2-disubstituted alkenes undergo effective hydroformylation with 89-97% ee and complete conversion for six examples. Palladium-catalyzed aerobic oxidative amination of allyl benzyl ether followed by enantioselective hydroformylation yields the β3-aminoaldehyde with 74% ee.

The use of nonactivated iminodienophiles in the stereoselective aza-Diels-Alder reaction

This paper describes the preparation of nitrogen-containing bicycles by the aza-Diels-Alder reaction of nonactivated iminodienophiles and cyclopentadiene. Readily available starting materials such as (S)-(-)-lactate and L-amino acids were used for the pre

Tetraallylstannane and Weinreb amides: A simple 'green' route to N-protected homoallylic alcohols and allyl ketones

We have explored the addition of tetraallylstannane (7) to a variety of N-protected Weinreb amides (N-phthalimido and N-benzyl). Reactions were conducted in methanol and the ionic liquid, butylmethylimidazole tetrafluoroborate (bmim[BF4]), yields of the corresponding N-protected allylketones were moderate to good. Allylation of the corresponding aminoaldehydes gave excellent yields of homoallylic alcohols (68-94%) and moderate to good diastereoselectivities (50-86%). (C) 2000 Published by Elsevier Science Ltd.

Highly enantioselective hydroformylation of olefins catalyzed by rhodium(I) complexes of new chiral phosphine-phosphite ligands

A new chiral phosphine-phosphite ligand, (R)-2-(diphenylphosphino)- 1,1'-binaphthalen-2'-yl (S)-1,1'-binaphthalene-2,2'-diyl phosphite [(R,S)- BINAPHOS, (R,S)-2a], was synthesized. Its Rh(I) complex was prepared, and its structure has been characterized by 1H and 31P NMR spectroscopy. Using Rh(I) complexes of (R,S)-2a and its enantiomer, highly enantioselective hydroformylation of styrene has been performed (94% ee, iso/normal = 88/12). The catalyst system was also effective for a variety of other olefins. Some other phosphine-phosphite ligands bearing 1,1'-binaphthyl and biphenyl backbones, such as (S)-3,3'-dichloro-6-(diphenylphosphino)-2,2',4,4'- tetramethylbiphenyl-6'-yl (R)-1,1'-binaphthalene-2,2'-diyl phosphite [(S,R)- BIPHEMPHOS. (S,R)-5a], (R,R)-2a, (R,S)-2b, (R)-2c, and (R)-5b, were tested for asymmetric hydroformylation. The results indicate that the sense of enantioface selection for the prochiral olefins is mainly determined by the absolute configuration of the phosphine site, for example, the (R)-2- (diphenylphosphino)-1,1'-binaphthalen-2'-yl group in (R,S)-2a. The relative configurations of the two biaryl groups in the phosphine-phosphites play crucial roles in the degree of the enantioselectivities, that is, the (R,S)- isomer generally gives products in high ee's and the (R*,R*)-isomer does in low ee's. Treatment of Rh(acac)[(R,S)-2a] with a 1:1 mixture of carbon monoxide and hydrogen gave a hydridorhodium complex. RhH-(CO)2[(R,S)-2a], as a single species. Trigonal bipyramidal structure is suggested for this complex, in which the hydride and the phosphite moiety are located at the apical positions and the phosphine and the two carbonyls occupy the equatorial positions. The interchange of the phosphine and the phosphite sites with each other through rapid pseudorotations has not been observed in RhH(CO)2[(R,S)-2a]. The structural deviations of the monohydride complexes from an ideal trigonal bipyramid seem to be larger in (R*,R*)-isomers than in the corresponding (R*,S*)-isomers. The existence of only one active species involved in the Rh(1)-(R,S)-2a-catalyzed hydroformylation has been manifested by the plot of ln([R]/[S]) of the hydroformylation product vs the reciprocals of the reaction temperatures. The higher thermodynamic stability of Rh(acac)[(R,S)-2a] than its diastereomer Rh(acac)[(R,R)-2a] is demonstrated in relation to the restricted configuration of (R)-2c to (R,S)- 2c in its complex formation with Rh(1).

STEREOCHEMISTRY OF THIAZOLIDINE RING FORMATION FROM AMINALS AND CYSTEINE

Aminals derived from Z-S-Ala, Z-R-Ala and Pht-S-Ala were coupled with R- and S-cysteine to give thiazolidine analogues of dipeptides with the configuration of the newly formed stereogenic carbon depending on the alanine configuration. 1H-NMR and CD spectr

Asymmetric Hydroformylation Catalyzed by Homogeneous and Polymer-Supported Platinum Complexes Containing Chiral Phosphine Ligands

A complex of Pt(II) containing the chiral ligand (2S,4S)-N-(tert-butoxycarbonyl)-4-(diphenylphosphino)-2-pirrolidine in the presence of stannous chloride catalyzed the hydroformylation of a variety of prochiral olefins.Although the branched/normal (b/n) ratios were low (ca. 0.5), high ee's were achieved in the hydroformylation of styrene (70-80percent), p-isobutylstyrene (80percent), 2-vinylnaphthalene (77percent), 2-ethenyl-6-methoxynaphthalene (81percent), 4-(2-thienylcarbonyl)styrene (78percent), vinyl acetate(82percent), N-vinylphthalimide (73percent), methyl methacrylate (60percent), and norbornene (60percent).When the hydroformylation of styrene, 2-ethenyl-6-methoxynaphthalene, and vinyl acetate with PtCl2/SnCl2 was carried out in the presence of triethyl orthoformate, enantiomerically pure acetals were obtained.The hydroformylation in the presence of ethyl orthoformate also could be carried out by using a catalyst containing the PtCl2/SnCl2 complex bound to 60-μm beads composed of cross-linked polystyrene.