不对称diels-Alder反应中的手性催化剂

本文综述了近年来不对称Diels-Alder反应中手性催化剂研究的进展,对各类手性催化剂的性能和特点作了简要介绍.     

Catalyzed asymmetric diels-alder reaction of benzoquinone. Total synthesis of (-)-ibogamine

The Diels-Alder addition of diene 2 with benzoquinone catalyzed by (S)-BINOL-TiCl(2) produced cycloadduct 5 in >65% yield and 87% ee. The cycloadduct was transformed into (-)-ibogamine in nine steps (10% overall yield from benzoquinone). A model for the transition state leading to 5 is proposed.     

新的手性β-亚磺酰亲双烯体用于不对称Diels-Alder反应

手征性cis-β-亚磺酰丙烯酸酯可从(1R, 2S, 3R)-3-巯基-1,7,7-三甲基二环[2.2.1]庚-2-醇制备, 它与环戊二烯的反应得Diels-Alder加成物, 并具有相当高的端基差向异构选择性。     

Stereochemical aspects of asymmetric diels-alder reaction catalyzed by chiral alkoxyaluminum dichlorides

Clear stereochemical relationships were observed between the structure of chiral sources of catalysts and absolute configuration of the Diels-Alder adducts.     

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

Remarkably high diastereoselectivity is observed in the organoaluminum catalyzed asymmetric Diels-Alder reaction of (-)-dimenthyl fumarate.     

Tandem hetero diels-alder reaction: synthesis of oxygenated macrocycles

[structure: see text]. C2-symmetric, oxygenated macrocycles have been synthesized from simple acyclic precursors in a single step by a tandem hetero Diels-Alder reaction. Thermolysis and Lewis acid catalysis can effect this novel transformation. The tandem reaction product is formed in preference to the intramolecular cycloaddition product, and an explanation for this result is proposed.     

Control elements in the intramolecular diels-alder reaction: synthesis of α-eudesmol

Triene $\text{1}$ undergoes cyclization with substantial 1,3 and 1,4 chiral induction to give largely trans, equatorial α-eudesmol $\text{3}$.     

Pyranophane transannular diels-alder approach to (+)-chatancin: a biomimetic asymmetric total synthesis

An asymmetric total synthesis of (+)-chatancin was achieved via a transannular Diels-Alder (TADA) reaction of an in situ generated macrocyclic pyranophane pseudobase. The presented route constitutes the second of two proposed biosynthetic pathways that involves a TADA reaction. It links this diterpene biogenetically to the cembranoids. A set of TADA selection rules that rationalize the formation of (+)-chatancin from a dynamic equilibrium of four 2-hydroxy-2H-pyrane bicycles and their 16 potential TADA transition states are also outlined. Beyond the TADA reaction, highlights of the synthetic work include the assembly of a chiral acyclic macrocyclization substrate from (S)-citronellol and an efficient macrocyclization via a beta-ketosulfoxyde/enone Michael addition.     

Polycyclic hydroxyquinones-xix : Regiospecific synthesis of anthracyclinones via the diels-alder reaction with dichloronaphthazarins

A convenient route to the daunomycinone precursor 18via a succession of Diels-Alder reactions from 2,7-dichloronaphthazarin (9) is described. In a similar manner, starting from 2,6-dichloronaphthazarin (19) compound 20, a regioisomer of 18,is synthesized. This methodology constitutes a regiospecific approach to (±)-daunomycinone and related anthracyclinones.     

A thermal dehydrogenative diels-alder reaction of styrenes for the concise synthesis of functionalized naphthalenes

Functionalized naphthalenes are valuable building blocks in many important areas. A microwave-assisted, intramolecular dehydrogenative Diels-Alder reaction of styrenyl derivatives to provide cyclopenta[b]naphthalene substructures not previously accessible using existing synthetic methods is described. The synthetic utility of these uniquely functionalized naphthalenes was demonstrated by a single-step conversion of one of these cycloadducts to a fluorophore bearing a structural resemblance to Prodan.     

Structural manifestations of the retro diels-alder reaction

Examination of selected cyclohexene derivatives which are fixed into the boat conformation reveals structural deviations from "normal" C-C bond distances consistent with the early stages of the retro Diels-Alder reaction.     

A convenient synthesis of pyridazine-3,4-dicarboxylic acid by a hetero diels-alder reaction

A convenient route to prepare unsubstituted pyridazine-3,4-dicarboxylic acid on a preparative scale is described. The synthesis involves a hetero Diels-Alder reaction between a new 1,2-diaza-1,3-diene and ethyl vinyl ether and oxidation of the intermediate 1,4,5,6-tetrahydropyridazine as the key step.     

Type 2 intramolecular N-acylnitroso diels-alder reaction: stereoselective synthesis of bridged bicyclic oxazinolactams

[reaction: see text] The type 2 intramolecular N-acylnitroso Diels-Alder reaction has been employed for the synthesis of substituted bridged bicyclic oxazinolactams. Upon oxidation of hydroxamic acid 6, a 3-benzylated oxazinolactam (7) was synthesized with complete diastereoselectivity. Elaboration of cycloadduct 7 liberated a cis-3,7-disubstituted azocin-2-one (9).     

Intramolecular diels-alder reaction of iminothiol esters

Diels-Alder reaction of dienyl α-methacrylthioimidates has been investigated under thermal or Lewis acid or protonic acid catalysed conditions. The utility of the reaction is shown by desulfurative ring contraction of bicyclo[4.4.0] to bicyclo[4.3.0]system.     

1-Alkenyl- and 1-alkadienylsilatranes in the diels-alder reaction

Conclusions This is the first study of the behavior of 1-alkenyl- and 1-alkadienylsilatranes in the Dials—Alder reaction. The 1-alkenyl derivatives are rather active dienophiles in the reaction with cyclopentadiene and hexachlorocyclopentadiene. 1-Silatranyl-1,3-butadiene is a reactive diene in the reaction with tetracyanoethylene and maleic anhydride.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2792–2794, December, 1984.