Ni-Catalyzed asymmetric hetero-Diels–Alder reactions of conjugated vinyl azides: synthesis of chiral azido polycycles

Abstract

We report herein an efficient Ni(II)/Feng ligand-catalyzed asymmetric Hetero-Diels-Alder reaction between conjugated vinyl azides with carbonyl groups. This method provides a platform for the synthesis of complicated chiral azido polyclcles...

Feng chiralN,N′-dioxide ligands: uniqueness and impacts

“…55 Moreover, privileged Feng ligand-metal complexes have also provided facile access to a variety of structurally diverse nitrogenheterocyclic compounds via asymmetric cycloaddition reactions. 56,57,58,59 Huang and colleagues 60 achieved convergent synthesis of chiral vicinal amino alcohols via an enantioselective reductive radical-type coupling reaction of nitrones with aromatic ketyl radicals generated from photocatalyzed single-electron transfer reduction of carbonyls (Scheme 3e). Paton, Smith, and colleagues 61 recently demonstrated that the use of L 3 -PrPr 2 -Sc (OTf) 3 could lower the triplet energy of acrylanilides by forming complexes with the acrylanilides, to which selective energy transfer from a photosensitizer proceeded, thereby enabling an asymmetric 6π photocyclization reaction (Scheme 3f).…”

Advances in C—N3 Retention Reactions Involving Organic Azides

“…随后, 徐政虎课题组在 2021 年又报道了富电子的 共轭二烯基叠氮与含有活泼羰基的靛红的 HDA 反应 (Scheme 4), 以 Ni(ClO 4 ) 2 •6H 2 O 和 L3 为催化体系, 合成 了手性螺环氧化吲哚衍生物 [14] . 靛红的苯环上带有强 吸电子和给电子取代基时, 均可以优秀的产率(≥92%) 和对映选择性(≥95% ee)得到相应产物.…”

S-triggered Schmidt-type rearrangement of vinyl azides to access N-aryl-(trifluoromethylsulfinyl)acetamides

“…Vinyl azides, which are easily available substrates, 6 have attracted increasing attention as versatile building blocks 7 in the construction of various types of azaheterocycles. 8 Alternative transformations of vinyl azides include Schmidt-type rearrangement that quickly affords a variety of valuable amides (Scheme 2a). 9 With the advanced work of Jiao, Chiba and Bi, vinyl azides have emerged as an amide surrogate through C-induced rearrangement reactions mediated by Lewis acids (LA), furnishing amide products decorated by diverse functional groups (Scheme 2b).…”