Asymmetric diels-alder reaction. Cooperative blocking effect in organic synthesis

Furuta, Kyoji; Iwanaga, Kumi; Yamamoto, Hisashi

doi:10.1016/s0040-4039(00)84991-6

Cited by 94 publications

(33 citation statements)

References 9 publications

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“…8) According to Yamamoto's and Fleming's procedures, [8][9][10] the diastereoselective Diels-Alder reaction of 5-trimethylsilylcyclopentadiene 1 with di-(1R)-menthyl fumarate 2 was carried out in the presence of diethylaluminun chloride in toluene at Ϫ78°C to yield the corresponding (2S,3S)-norbornene-dicarboxylic acid di-(1R)-menthyl ester 3 bearing a trimethylsilyl group at the 7-exo position in a quantitative yield with a diastereomeric excess of 97%. A single recrystallization from ethanol gave optically pure di-(1R)-menthyl ester 3.…”

Section: Resultsmentioning

confidence: 99%

“…The MOM group of 10 was removed by treatment with trifluoroacetic acid, and the corresponding diphosphine 7-syn alcohol 11 was obtained in 74% yield. (2S,3S)-Norbornane diphosphine 14 bearing no hetero functional group at the 7-position was also prepared by phosphination of (2S,3S)-norbornanedimethanol dimesylate 13 which was prepared similarly via a synthetic intermediate reported by Yamamoto et al 8) By using two representative norbornane diphosphines 10 and 14 as chiral ligands, preliminary asymmetric hydrogenation of functionallized olefins, itaconic acid and (Z)-aacetamidocinnamic acid, was carried out with a cationic rhodium complex catalyst. The results are summarized in Table 1.…”

Section: Resultsmentioning

confidence: 99%

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Preparation of Enantiopure Norbornane Ligands Bearing Both (2S,3S)-Bis(phosphinomethyl) and 7-syn-Oxygen Functional Groups and an Application to Rhodium-Catalyzed Asymmetric Hydrogenation

Morimoto

Yamazaki

Achiwa

2004

CHEMICAL & PHARMACEUTICAL BULLETIN

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Development of efficient methods for the practical enantioselective synthesis of chiral compounds has been one of the most important subjects in synthetic organic chemistry. 1)Many kinds of enantioselective syntheses employing various catalysts such as metal complexes coordinated with chiral ligands have been reported for more than three decades, [1][2][3][4][5][6] and several optically pure compounds prepared by enantioselective synthesis with the chiral catalysts are now commercially available (e.g. optically pure a-amino acids or alcohols by using asymmetric hydrogenation with Rh-or Ru-chiral phosphine catalysts [3][4][5] ; L-menthol by using Rh-BINAP-catalyzed asymmetric isomerization of an allylamine 4) ) and are used as chiral pools or auxiliaries for enantioselective syntheses. For the development of efficient chiral metal complex catalysts, the most significant strategy is based on the preparation of new useful chiral ligands. Various types of di-or mono-functionalized chiral ligands have been developed; for example, di-and mono-phosphines (P,P-or P-type), aminophosphines (P,N-type), diamine and amine (N,N-or N-type), etc. On the other hand, tri-or multi-functionalized ligands are much rarer. We previously reported in a preliminary communication the preparation of chiral norbornane derivatives bearing both diphosphine moieties and another hetero functional group. 7) In this article we describe in detail the synthesis of enantiomerically pure norbornane derivatives by employing both highly diastereoselective Diels-Alder reaction and stereospecific frame rearrangement (Wagner-Meerwein type rearrangement) as the key steps, and an application to rhodium-catalyzed asymmetric hydrogenation. Results and DiscussionThe synthetic route to several optically pure norbornane derivatives bearing (2S)-and (3S)-substituents and an oxygen functional group at the 7-syn position is described in Chart 1. Yamamoto and co-workers reported an efficient Diels-Alder reaction of cyclopentadiene with an optically pure dimenthyl fumarate for the preparation of optically active norbornene derivatives.8) According to Yamamoto's and Fleming's procedures, [8][9][10] the diastereoselective Diels-Alder reaction of 5-trimethylsilylcyclopentadiene 1 with di-(1R)-menthyl fumarate 2 was carried out in the presence of diethylaluminun chloride in toluene at Ϫ78°C to yield the corresponding (2S,3S)-norbornene-dicarboxylic acid di-(1R)-menthyl ester 3 bearing a trimethylsilyl group at the 7-exo position in a quantitative yield with a diastereomeric excess of 97%. A single recrystallization from ethanol gave optically pure di-(1R)-menthyl ester 3. Halolactonization of the norbornene diester 3 was carried out with bromine to give a bromolactone 4 (97%) with selective participation of the carbonyl group of the 2-endo ester. The bromolactone 4 was allowed to rearrange stereospecifically with silver nitrate in methanol according to Fleming's procedure.9,10) The corresponding (2S,3S)-norbornene dicarboxylate 5 having a 7-syn hydroxyl group was obtaine...

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Preparation of Enantiopure Norbornane Ligands Bearing Both (2S,3S)-Bis(phosphinomethyl) and 7-syn-Oxygen Functional Groups and an Application to Rhodium-Catalyzed Asymmetric Hydrogenation

Morimoto

Yamazaki

Achiwa

2004

CHEMICAL & PHARMACEUTICAL BULLETIN

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“…As a result of the cooperation of both prosthetic groups, 12 very high diastereoselectivity (>97% de, 93% (1a) to (−)-3 in apolar solvents such as n-hexane. A good linear correlation between the diastereoselectivity and the solvatochromic properties of the solvent was found, but, in contrast to the sultam analog (−)-2, dienophile (−)-3 exhibits opposite and increasing selectivity in apolar solvents.…”

Section: Resultsmentioning

confidence: 99%

Asymmetric induction in the [4+2]cycloaddition of cyclopentadiene and furan to chiral derivatives of fumaric acid

et al. 2001

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“…4 In large-scale processes, as in industrial production, use of the expensive and toxic brucine can be avoided by preparing (-)-(S,S)-2 in 99% enantiomeric excess (ee) via a Lewis acid-catalyzed cycloaddition of di-(-)-menthyl fumarate to anthracene. 5 By changing di-(-)-menthyl fumarate to di-(+)-isomenthyl fumarate in the asymmetric Diels-Alder reaction, the (+)-(R,R)-form of 2 can be obtained (Thunberg and Allenmark. Asymmetric cycloaddition routes to both enantiomers of trans-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboxylic acid.…”

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confidence: 99%

Evaluation of a chiral stationary phase derived from a simple Diels‐Alder reaction

Thunberg

Allenmark

2003

Chirality

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The bicyclic, C(2)-symmetric dicarboxylic acid obtained from the cycloaddition of fumaric acid to anthracene can readily be prepared in enantiomerically pure form on a large scale. Conversion of either enantiomer of the diacid into its corresponding bis-allylamide yields a selector unit, used as a building block in the synthesis of a chiral stationary phase (CSP). The terminal C-C double bonds in the selector unit were used in a hydrosilylation reaction involving a multifunctional hydrosilane to effect polymerization, crosslinking, and immobilization to the vinyl-silica used as support. A study of the enantiomer-discriminating abilities of the new CSP was made. Large separation factors were obtained for a series of benzodiazepinones, which were studied in further detail by the use of different retention modifiers. To some extent, rationalization of retention data has been achieved in terms of competition for hydrogen bonding.

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Asymmetric diels-alder reaction. Cooperative blocking effect in organic synthesis

Cited by 94 publications

References 9 publications

Preparation of Enantiopure Norbornane Ligands Bearing Both (2S,3S)-Bis(phosphinomethyl) and 7-syn-Oxygen Functional Groups and an Application to Rhodium-Catalyzed Asymmetric Hydrogenation

Preparation of Enantiopure Norbornane Ligands Bearing Both (2S,3S)-Bis(phosphinomethyl) and 7-syn-Oxygen Functional Groups and an Application to Rhodium-Catalyzed Asymmetric Hydrogenation

Asymmetric induction in the [4+2]cycloaddition of cyclopentadiene and furan to chiral derivatives of fumaric acid

Evaluation of a chiral stationary phase derived from a simple Diels‐Alder reaction

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