パラジウム触媒による環化を伴うアリール化反応の研究

京都大学0048新制・課程博士博士(理学)甲第18097号理博第3975号新制||理||1573(附属図書館)30955京都大学大学院理学研究科化学専攻(主査)准教授 依光 英樹, 教授 丸岡 啓二, 教授 大須賀 篤弘学位規則第4条第1項該当Doctor of ScienceKyoto UniversityDGA

Palladium-catalysed arylative cyclisation of N-allylacetamides with aryl halides yielding benzyl-substituted oxazolines

Treatment of N-allylacetamide with aryl halide in the presence of sodium t-butoxide and a palladium catalyst leads to arylative cyclisation to provide the corresponding benzyl-substituted oxazoline in high yield

Palladium-catalyzed cross-coupling of unactivated aryl sulfides with arylzinc reagents under mild conditions.

Cross-coupling of general aryl alkyl sulfides with arylzinc reagents proceeds smoothly, even at room temperature or below, with a palladium-N-heterocyclic carbene (NHC) catalyst. When combined with reactions that are unique to organosulfurs, that is, the SNAr sulfanylation or Pummerer reaction, the cross-coupling offers interesting transformations that are otherwise difficult to achieve. An alkylsulfanyl group is preferentially converted whilst leaving the tosyloxy and chloro intact, which expands the variety of orthogonal cross-coupling

Synthesis of 1,2-Disubstituted Cyclopentenes by Palladium-Catalyzed Reaction of Homopropargyl-Substituted Dicarbonyl Compounds with Organic Halides via 5-<i>Endo-Dig</i> Cyclization

Palladium catalysts with bulky biaryl phosphine ligands allow homopropargyl-substituted dicarbonyl compounds to undergo intramolecular addition via a rare 5-<i>endo-dig</i> pathway. C–C bond forming reductive elimination follows the addition to introduce alkenyl and alkynyl as well as aryl groups by using the corresponding organic halides. The cyclization is versatile enough to be applicable to the synthesis of highly substituted dihydropyrrole and a fused tricyclic compound

Regiocontrolled Palladium-Catalyzed Arylative Cyclizations of Alkynols

Tuning the reactivity of arylpalladium intermediates enables control of catalytic arylative <i>5-exo</i> and <i>6-endo</i> cyclizations of alkynols. The two modes of cyclizations represent a rare example of controllable, regioselective difunctionalization of alkynes. The cyclizations are useful in offering a divergent synthesis of oxygen-containing heterocycles, which is of synthetic use for further derivatization. Formal synthesis of an hNK-1 receptor antagonist also showcases the utility of our arylative cyclization

Synthesis of 1,2-Disubstituted Cyclopentenes by Palladium-Catalyzed Reaction of Homopropargyl-Substituted Dicarbonyl Compounds with Organic Halides via 5-<i>Endo-Dig</i> Cyclization

Palladium catalysts with bulky biaryl phosphine ligands allow homopropargyl-substituted dicarbonyl compounds to undergo intramolecular addition via a rare 5-<i>endo-dig</i> pathway. C–C bond forming reductive elimination follows the addition to introduce alkenyl and alkynyl as well as aryl groups by using the corresponding organic halides. The cyclization is versatile enough to be applicable to the synthesis of highly substituted dihydropyrrole and a fused tricyclic compound