Competitive Intramolecular Diels - Alder Reactions of bis-α,β-Unsaturated Ester Derivatives of Enzymatically Derived and Enantiopure cis-1,2-Dihydrocatechols. Enantiodivergent Synthesis of Monochiral Bicyclo[2.2.2]oct-2-enes

2003 ◽  
Vol 56 (9) ◽  
pp. 861 ◽  
Author(s):  
Martin G. Banwell ◽  
Cai Chun ◽  
Alison J. Edwards ◽  
Markus M. Vögtle
Keyword(s):  
Natural Products ◽  
Single Crystal ◽  
Building Blocks ◽  
Diels Alder ◽  
Unsaturated Ester ◽  
Enantiomerically Pure ◽  
X Ray ◽  
Derivatives Of ◽  
Natural Products Synthesis

bis-Crotonate and related α,β-unsaturated ester derivatives of readily available and enantiomerically pure cis-1,2-dihydrocatechols engage, upon heating in refluxing toluene, in two competitive intramolecular Diels–Alder reactions to give varying mixtures of chromatographically separable and pseudo-enantiomeric bicyclo[2.2.2]oct-2-enes. Such adducts, many of which have been characterized by single-crystal X-ray analysis, are likely to serve as useful building blocks in natural products synthesis.

scholarly journals Preparation of O-Methyl Substituted 2-Oxofuro- and 2-Oxopyrrolidinoindolines by Reductive Lactonization of Oxindol-3-Ylacetic Acids

2012 ◽  
Vol 7 (11) ◽  
pp. 1934578X1200701
Author(s):  
Martha S. Morales-Ríos ◽  
Ernesto Rivera-Becerril ◽  
Perla Y. López-Camacho ◽  
Nadia A. Pérez-Rojas ◽  
Oscar R. Suárez-Castillo
Keyword(s):  
Natural Products ◽  
Single Crystal ◽  
X Ray ◽  
Practical Procedure ◽  
Natural Products Synthesis

A practical procedure for the preparation of O-methyl substituted 3a,8-dialkyl-2-oxofuroindolines is described. Reductive lactonization of the corresponding oxindol-3-ylacetic acids provides a route for the formation of this class of compounds. Further transformation of 2-oxofuroindolines into 2-oxopyrrolidinoindolines, and then to pyrrolidinoindolines demonstrates their versatility as key intermediates in natural products synthesis. The results of single-crystal X-ray crystallographic analyses are given for five of the studied compounds.

Synthesis and Biological Evaluation of Some Enantiomerically Pure C8c - C15 Monoseco Analogues of the Phenanthroquinolizidine-Type Alkaloids Cryptopleurine and Julandine

2008 ◽  
Vol 61 (7) ◽  
pp. 506 ◽  
Author(s):  
Magne O. Sydnes ◽  
Anna Bezos ◽  
Christopher Burns ◽  
Irma Kruszelnicki ◽  
Christopher R. Parish ◽  
...  
Keyword(s):  
Single Crystal ◽  
Building Blocks ◽  
Biological Evaluation ◽  
Enantiomerically Pure ◽  
X Ray ◽  
System 1 ◽  
Synthesis And Biological Evaluation ◽  
Related Compounds

A series of enantiomerically pure C8c–C15 monoseco analogues, 23–30, of the alkaloids cryptopleurine (1) and julandine (2) have been prepared using cinnamyl chloride 37 and (S)- or (R)-2-methylpiperidine as key building blocks. Two related compounds, 31 and 32, have also been synthesized. Each of these analogues has been subjected to various biological evaluations and most of them show dramatically reduced cytotoxicity compared with parent system 1. Nevertheless, they are potent anti-angiogenic agents. The formation and single-crystal X-ray analysis of the spirocyclic dienone 54, a by-product arising from attempts to prepare analogue 32, is also described.

Biomimetic Synthesis of Hyperjapones F-I

2018 ◽  
Vol 71 (9) ◽  
pp. 649 ◽  
Author(s):  
Hiu C. Lam ◽  
Quang D. Phan ◽  
Christopher J. Sumby ◽  
Jonathan H. George
Keyword(s):  
Natural Products ◽  
Building Blocks ◽  
Diels Alder ◽  
Biomimetic Synthesis ◽  
Enantiomerically Pure ◽  
Biosynthetic Precursor ◽  
Hypericum Japonicum ◽  
Optical Rotations

Hyperjapones F–I are tetracyclic meroterpenoids recently isolated from Hypericum japonicum. All four of these natural products have been synthesised using oxidative, intermolecular hetero-Diels–Alder reactions to couple their common biosynthetic precursor, norflavesone, to the appropriate monoterpene building blocks: sabinene, β-pinene, and α-pinene. The synthesis of enantiomerically pure hyperjapones H and I and comparison of their optical rotations to those of the natural samples indicated that these meroterpenoids are probably biosynthesised as either racemic or scalemic mixtures.

Structural Study of an Unusual Diels-Alder Adduct

1992 ◽  
Vol 45 (12) ◽  
pp. 2089 ◽  
Author(s):  
EL Ghisalberti ◽  
BW Skelton ◽  
AH White
Keyword(s):  
Single Crystal ◽  
Diffraction Study ◽  
Structural Study ◽  
Spectroscopic Studies ◽  
Diels Alder ◽  
X Ray Diffraction ◽  
X Ray ◽  
Naturally Occurring ◽  
Chemical Evidence ◽  
Alder Adduct

The structure of the compound obtained on heating the naturally occurring clerodane furanoditerpene (1) had been formulated as (2) on the basis of spectroscopic studies. A single-crystal X-ray diffraction study on the dihydro derivative of (2) has confirmed this and provides support for the stereochemistry previously assigned to (1) on the basis of chemical evidence.

First practical synthesis of enantiomerically pure (R)- and (S)-desmethylsibutramine (DMS) and unambiguous determination of their absolute configuration by single-crystal X-ray analysis

2002 ◽  
Vol 13 (2) ◽  
pp. 107-109 ◽  
Author(s):  
Zhengxu Han ◽  
Dhileepkumar Krishnamurthy ◽  
Derek Pflum ◽  
Qun K. Fang ◽  
Hal Butler ◽  
...  
Keyword(s):  
Single Crystal ◽  
Absolute Configuration ◽  
Enantiomerically Pure ◽  
X Ray ◽  
Unambiguous Determination ◽  
Practical Synthesis

scholarly journals Synthesis and Optoelectronic Properties of Iptycene–Naphthazarin Dyes

Synlett ◽  
2018 ◽  
Vol 30 (01) ◽  
pp. 54-58 ◽  
Author(s):  
Timothy Swager ◽  
Cagatay Dengiz ◽  
You-Chi Wu
Keyword(s):  
Single Crystal ◽  
Electronic Properties ◽  
Diels Alder ◽  
Optoelectronic Properties ◽  
Synthesis And Characterization ◽  
Nmr Analysis ◽  
X Ray ◽  
Vis Spectroscopy

We report the synthesis and characterization of iptycene–naphthazarin dyes by using a sequential Diels–Alder approach. The tautomerization of naphthazarin was used as the key step in the synthesis, with structures confirmed by single-crystal X-ray and NMR analysis. The systematic trends in electronic properties were investigated by UV/Vis spectroscopy. BF2 complexes of the dyes were prepared by reaction with BF3·OEt2 in CH2Cl2.

New, Homochiral Synthons Obtained through Simple Manipulations of Enzymatically Derived 3-Halo-cis-1,2-dihydrocatechols

2015 ◽  
Vol 68 (10) ◽  
pp. 1467 ◽  
Author(s):  
Lorenzo V. White ◽  
Ping Lan ◽  
Brett D. Schwartz ◽  
Anthony C. Willis ◽  
Martin G. Banwell
Keyword(s):  
Single Crystal ◽  
Cycloaddition Reaction ◽  
Diels Alder ◽  
X Ray

The bromoepoxide 5a, which is obtained from the homochiral and enzymatically derived cis-1,2-dihydrocatechol 1a, is readily and efficiently transformed into either isomer 8a or the corresponding methoxymethyl-ether 2a. Though both of these products can be fully characterized, they are somewhat unstable, with the former being converted into the crystalline enone 3a on standing and the latter readily participating in a Diels–Alder cycloaddition reaction with the potent dienophile N-phenyl-1,2,4-triazoline-3,5-dione to give adduct 7a. The single-crystal X-ray structures of compounds 3a and 7a are reported. Using the related chemistry the chloro-analogue, 3b, of enone 3a can be obtained.

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