128822-07-1Relevant articles and documents
Scalable and Highly Diastereo- and Enantioselective Catalytic Diels-Alder Reaction of α,β-Unsaturated Methyl Esters
Gatzenmeier, Tim,Turberg, Mathias,Yepes, Diana,Xie, Youwei,Neese, Frank,Bistoni, Giovanni,List, Benjamin
supporting information, p. 12671 - 12676 (2018/10/15)
Despite tremendous advances in enantioselective catalysis of the Diels-Alder reaction, the use of simple α,β-unsaturated esters, one of the most abundant and useful class of dienophiles, is still severely limited in scope due to their low reactivity. We report here a catalytic asymmetric Diels-Alder methodology for a large variety of α,β-unsaturated methyl esters and different dienes based on extremely reactive silylium imidodiphosphorimidate (IDPi) Lewis acids. Mechanistic insights from accurate domain-based local pair natural orbital coupled-cluster (DLPNO-CCSD(T)) calculations rationalize the catalyst control and stereochemical outcome.
Stereocontrolled Diels-Alder Reactions with Chiral Tricyclic Oxazolidinones
Tanaka, Kazuhiko,Uno, Hiroe,Osuga, Hideji,Suzuki, Hitomi
, p. 629 - 632 (2007/10/02)
(1R,2R,6S,7S)-5-Aza-1,10,10-trimethyl-3-oxatricyclo2,6>decan-4-one (endo-oxazolidinone) and (1R,2R,6R,7S)-isomer (exo-oxazolidinone) are found to be efficient diastereomeric auxiliaries for Diels-Alder reactions, which are promoted by L
(5R)-7,8:9,10-Di-O-isopropylidene-2,6-dioxa-4-azaspirodecan-3-one: A New Chiral Spirooxazolidin-2-one derived from D-(+)-Galactose for use in Asymmetric Transformations
Banks, Malcolm R.,Blake, Alexander J.,Cadogan, J. I. G.,Dawson, Ian M.,Gaur, Suneel,et al.
, p. 1146 - 1148 (2007/10/02)
Starting from D-(+)-galactose, the crystalline spirooxazolidin-2-one 2 can be readily prepared in an optically pure state by a nitrene-mediated four-step sequence, and serves to control both aldol and Diels-Alder reactions with high chiral efficiency, being easy to remove after use.
Enantiospecific preparation of [(2R,6S)-endo]-5-aza-1,10,10-trimethyl-3-oxatricyclo[5.2.1.02,6)]de can-4-one by a nitrene-mediated route from [(1S]-endo]-(-)-borneol and its utility as a chiral auxiliary in some asymmetric transformations
Banks,Blake,Cadogan,Dawson,Gosney,Grant,Gaur,Hodgson,Knight,Smith,Stevenson
, p. 7979 - 8006 (2007/10/02)
Attempted chiral aziridination of styrene by addition of optically-active alkoxycarbonylnitrene 5 derived from [(1S)-endo]-(-)-bornyl p-nitrobenzenesulphonoxycarboxy 4 is reported. No measurable asymmetric induction is observed under the various conditions employed, but in the absence of alkene, a tricyclic oxazolidin-2-one 8 is formed to which preparatively simpler access can be gained by thermal decomposition of azidoformate 7, either in 1,1,2,2-tetrachloroethane (50%) or by spray pyrolysis (58%). The oxazolidin-2-one 8 is demonstrated to be a successful chiral auxiliary by contemporary standards in a variety of asymmetric transformations, including alkylation, acylation, and aldol reactions for which high levels of asymmetric induction are observed. Diethylaluminium chloride catalysed Diels-Alder reactions exhibit poorer selectivity except for the cinnamoyl derivative 23 which is stereospecific.
Asymmetric Diels-Alder Reaction with use of (S)-5-(Trityloxymethyl)pyrrolidin-2-one as a Chiral Auxiliary
Tomioka, Kiyoshi,Hamada, Noriko,Suenaga, Toshiro,Koga, Kenji
, p. 426 - 428 (2007/10/02)
(S)-5-(Trityloxymethyl)pyrrolidin-2-one (1) is an efficient and recyclable chiral auxiliary in the asymmetric Diels-Alder reaction of the imide (2) with dienes, affording cycloadducts (3) with excellent diastereofacial selectivity.
