A Catalytic Cross‐Olefination of Diazo Compounds with Sulfoxonium Ylides

Abstract

A ruthenium‐catalysed cross‐olefination of diazo compounds and sulfoxonium ylides is presented. Our reaction design exploits the intrinsic difference in reactivity of diazo compounds and sulfoxonium ylides as both carbene precursors and nucleophiles, which results in a highly selective reaction.

Ruthenium Catalyzed C−H Acylmethylation of N‐Arylphthalazine‐1,4‐diones with α‐Carbonyl Sulfoxonium Ylides: Highway to Diversely Functionalized Phthalazino‐fused Cinnolines

“…On the basis of our preliminary mechanistic results and literature precedents, a plausible mechanism for the o ‐acylmethylation and the two disclosed cyclizations are proposed (Scheme ). The reaction is believed to be initiated by the formation of active monomeric Ru II catalyst, {[RuX 2 ( p ‐cymene)]; X=PF 6 and/or Cl} by the dissociation of dimeric [RuX 2 ( p ‐cymene)] 2 with KPF 6 .…”

“…On the basis of our preliminary mechanistic resultsa nd literature precedents, [14,15,19,20] ap lausible mechanism for the oacylmethylation and the two disclosed cyclizationsa re proposed (Scheme 9). The reactioni sb elieved to be initiated by the formation of active monomeric Ru II catalyst, {[RuX 2 (pcymene)];X = PF 6 and/or Cl} by the dissociation of dimeric [RuX 2 (p-cymene)] 2 with KPF 6 .C yclometalation of this Ru II catalyst with 1a generates the five-membered ruthenacyclic intermediate A via CÀHa ctivation, which upon coordinationw ith sulfoxonium ylide (2)and subsequent eliminationofD MSO furnishes ar uthenium a-oxo carbene species B.T hereafter,m igratory insertion of the activated carbenei nto Ru-aryl bond gives as ix-memberedr uthenacyclic intermediate C,w hich upon protonolysis of the RuÀNa nd RuÀCb onds produces o-acylmethylated product 3,along with the regeneration of the active catalyst.…”

“…LR (1 (Table 2, entries [14][15]. Albeitn of urther change was observed by using 3equiv of BF 3 ·OEt 2 (Table 2, entry 16).…”

“…presentedt he cross-olefination of diazo compounds with sulfoxonium ylides under Ru-catalyzed conditiont oa fford Z-olefins (Scheme 1d). [15] Very recently,Z hou, Liu and their co-workersr eported Ru-catalyzed selective CÀHb ond activation of imidamides and annulation of sulfoxonium ylides to furnish 3-ketoindole derivatives in good yields (Scheme1e). [16] Interestingly,t he functionalization of phthalazine-diones with a-carbonyl sulfoxonium ylides remains unexplored.…”

Rh2(esp)2‐Catalyzed Coupling of α‐Diazo‐γ‐butyrolactams with Aromatic Amines

“…The chemistry of α‐diazocarbonyl compounds has attracted much attention from the synthetic organic and medicinal chemistry community, as it offers a wealth of powerful synthetic transformations including those which involve generation of metal carbene species , . One such transformation, allowing for direct functionalization of a carbo‐ or heterocyclic core, is the formal insertion of metal carbenes into the N–H bond of aromatic and aliphatic amines, amides, as well as azaheterocycles , .…”