Stereoselectivity in the TiCl4-Catalyzed [4+2] Cycloaddition of Cyclopentadiene to (2R)-Bornane-10,2-sultam Derivatives of Fumaric Acid Monoesters

Achmatowicz, Michal; Chapuis, Christian; Rzepecki, Piotr; Jurczak, Janusz

doi:10.1002/(sici)1522-2675(19990210)82:2<182::aid-hlca182>3.0.co;2-p

Cited by 9 publications

(2 citation statements)

References 16 publications

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“…The induced absolute configuration of the cycloadducts is based on the chiroptical properties in CHCl 3 of the corresponding diols (‐)‐(1 R ,2 S ,3 S ,4 S )‐ 5 , and (‐)‐(11 S ,12 S )‐ 7 ,,, (These diastereoisomers exhibit opposite chiroptical properties in either EtOH, or MeOH), as obtained after quantitative LiAlH 4 reduction of either the corresponding diesters 4 , or 6 with quantitative recovery of the prosthetic groups. The diastereoselectivity was determined on the crude cycloadducts by 1 H‐NMR analyses by integration of the vinyl protons at ca .…”

Section: Resultsmentioning

confidence: 99%

Diels‐Alder Reaction of Cyclopenta‐1,3‐diene and Anthracene to bis‐Fumarates Derived from Menthol Analogues

Piątek

Chapuis

2019

ChemistrySelect

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Due to steric interactions of the overly bulky substituted 8position, the classic 8-Ph-menthol (-)-1 d is not the optimal chiral auxiliary for the asymmetric Diels-Alder reaction of its bis fumarate (-)-2 d to dienes such as cyclopenta-1,3-diene 3 b, or anthracene 3 c. This prosthetic group (-)-1 d could efficiently be replaced by an intermediate smaller analog (-)-1 e, readily prepared in a single step by cyclopropanation of isopulegol (-)-1 b. This latter auxiliary, resulting from the industrial technology developed by Takasago for menthol (-)-1 a, does not necessitate the stereoselective ketone reduction and chromatographic separation of the usual Michael adducts, derived from (+)-pulegone. This chiral auxiliary (-)-1 e, never used as an asymmetric Diels-Alder promoter, is much more selective than menthol (-)-1 a itself, under uncatalyzed conditions, and is also more stable than the polymerizable isopulegyl derived dienophiles, under Lewis acid mediated conditions. This prosthetic group thus readily allows large scale operations in both accessible enantiomeric series. Results and DiscussionThe series of known chiral auxiliaries menthol (-)-1 a, [60][61] isopulegol (-)-1 b, [62][63][64] 8-Me-menthol (-)-1 c ([α] D 20 =-38.5, c = 1.0, CHCl 3 . For several signals, our 13 C-NMR attributions based [a]

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Section: Resultsmentioning

confidence: 99%

Diels‐Alder Reaction of Cyclopenta‐1,3‐diene and Anthracene to bis‐Fumarates Derived from Menthol Analogues

Piątek

Chapuis

2019

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“…cycloaddition reaction. 115 In contrast to the application of other auxiliaries, 116 a strong effect and a correlation between the increasing solvent polarity and p-facial selectivity was found during the uncatalyzed cycloaddition of (À)-164b to cyclopentadiene in the aforementioned protocol (Scheme 45).…”

Section: Halohydrin Reactionsmentioning

confidence: 99%

Recent advances in the application of the Oppolzer camphorsultam as a chiral auxiliary

Heravi

Zadsirjan

2014

Tetrahedron: Asymmetry

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Saturated Heterocycles as Chiral Auxiliaries

Październiok‐Holewa¹,

Stecko²

2022

Chiral Building Blocks in Asymmetric Synthesis

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Stereoselectivity in the TiCl4-Catalyzed [4+2] Cycloaddition of Cyclopentadiene to (2R)-Bornane-10,2-sultam Derivatives of Fumaric Acid Monoesters

Cited by 9 publications

References 16 publications

Diels‐Alder Reaction of Cyclopenta‐1,3‐diene and Anthracene to bis‐Fumarates Derived from Menthol Analogues

Diels‐Alder Reaction of Cyclopenta‐1,3‐diene and Anthracene to bis‐Fumarates Derived from Menthol Analogues

Recent advances in the application of the Oppolzer camphorsultam as a chiral auxiliary

Saturated Heterocycles as Chiral Auxiliaries

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