Divergent Reactivity of Phosphorylated and Related Allenes: [4 + 2] Cycloaddition with 3,6-Diphenyltetrazine, Self-Addition Leading to Dimers and [Pd]-Complex Formation.

Phosphorus-based naphthalenes are formed by self-dimerization-cum-cyclization of α-aryl allenylphosphonates or allenylphosphine oxides using catalytic Pd(OAc)2in the presence of PPh3 and Et3N . This reaction involves [4 + 2]-cycloaddition with the (ß,γ) double bond of one allene as the dienophile; the double bonds at the α-aryl-(ß',γ') group and (α,ß)-carbons of the second allene act as the diene part. A subsequent proton shift also takes place. Upon treating allenylphosphine oxides with Pd(OAc)2 [stoichiometry 2:1] in the presence of PPh3/Ag2CO3, a [Pd]-complex is isolated and structurally characterized. This complex can be used as a catalyst for C-C bond-forming reactions of phosphorus-based allenes with 2-iodophenol. Densely substituted 3,6-diphenylpyridazines are conveniently obtained in excellent yields by a thermally induced regioselective Inverse Electron Demand Diels-Alder (IEDDA) reaction of allenes with 3,6-diphenyltetrazine, followed by a [1,3]-H shift.

Palladium-catalysed cyclisation of ynamides and propargyl tethered iodosulfonamides with boronic acids leading to benzosultams.

An efficient and straightforward Pd-catalysed synthesis of diversely substituted sultams utilising ynamides and boronic acids is disclosed; toluene was found to be the most suitable solvent for this transformation. This strategy has been successfully applied to generate dihydrobenzo[d]isothiazole 1,1-dioxides and dihydro-2H-benzo[e][1,2]thiazine 1,1-dioxides. The advantages of this protocol are good functional group tolerance, broad substrate scope, high-yielding reaction and low catalyst loading to access benzofused sultams with five-/six-membered rings. The synthetic utility has been demonstrated by a gram-scale synthesis. A plausible catalytic cycle involving carbopalladation has been proposed for this transformation.

Cu(i) catalysed annulation of isothiocyanates/isocyanates with 2-iodo-sulfonamides: synthesis of benzodithiazines, benzothiadiazinones, benzothiazinylidene-anilines and benzothiazolylidene-anilines.

An efficient Cu(i)-catalysed cyclisation reaction of 2-iodobenzene sulfonamides with aryl-isothiocyanates and isocyanates that affords functionalised benzodithiazines and benzothiadiazinones, respectively, has been developed. Thus, in the reaction with aryl isothiocyanates (Ar-N[double bond, length as m-dash]C[double bond, length as m-dash]S), the C[double bond, length as m-dash]S moiety participates in the cyclisation leading to a dithiazine. By contrast, in the case of aryl isocyanates (Ar-N[double bond, length as m-dash]C[double bond, length as m-dash]O), the N[double bond, length as m-dash]C part is involved in the cyclisation and a thiadiazinone is obtained. Analogous reactions of isothiocyanates with N-tosyl-2-iodo-anilines and 2-iodo-benzyl sulfonamides afford (benzothiazin-2-ylidene)anilines and (benzothiazol-2-ylidene)anilines, respectively. Probable mechanistic pathways are briefly discussed.

Ethanol as a Hydrogenating Agent: Palladium-Catalyzed Stereoselective Hydrogenation of Ynamides To Give Enamides.

Ethanol is shown to act as a hydrogenating agent for ynamides under palladium catalysis. This behavior is different from the normally expected reaction of ethanol addition to alkynes. The reaction shows stereoselectivity for E enamides, which is in contrast to reports using other hydrogenating sources. The method was also extended to ynamines. Alternatively, the use of ethanol and ammonium formate as the hydrogenating source gives Z enamides. The role of ethanol in hydrogenation was demonstrated by means deuterium labeling experiment.

Exploring the gold mine: [Au]-catalysed transformations of enynals, enynones and enynols.

Gold catalysed synthesis of carbo-/hetero-cyclic compounds is currently a topic of intense activity thanks to the unique properties bestowed upon gold by relativistic effects, the potential of which has been realised mainly during the past two decades. This review will dwell upon the reactions involving gold catalysis in which enynal, enynone or enynol is one of the reacting partners. Most often these reactions lead to fused hetero-/homo-cycles under mild conditions with environmentally benign byproducts. Thus an opportunity for the organic community to develop new methodologies, efficient asymmetric variants, and application in total synthesis by [Au]-catalysis has emerged.

Transition Metal-Free Cascade Cyclization of Epoxy-Ynamides: To Go for 1,3-Oxazines or 1,4-Oxazines?

An approach to both 1,3- and 1,4-oxazines is developed by the cascade cyclization of epoxy ynamides under transition metal-free conditions. Thus, while 1,3-oxazines are obtained in a regio- and stereoselective manner by using base, cyclization of epoxy ynamides with sodium azide as a nucleophile results in 1,4-oxazines. Deuterium-labeling experiment demonstrates the role of water as a proton source in the formation of 1,4-oxazines. Epoxy tethered alkyne precursors provide 1,4-oxazines that undergo click reaction.

Use of Elemental Sulfur or Selenium in a Novel One-Pot Copper-Catalyzed Tandem Cyclization of Functionalized Ynamides Leading to Benzosultams.

A novel and efficient [Cu]-catalyzed one-pot regio- and stereospecific synthesis of benzo[1,4,2]dithiazine 1,1-dioxides and benzo[1,4,2]thiaselenazine 1,1-dioxides by cyclization of functionalized ynamides with elemental sulfur/selenium has been developed. Its generality is elegantly illustrated by extension to benzodithiazepines and benzothiaselenazepines. Involvement of water in the reaction is demonstrated by the incorporation of (2)D at the olefinic site by using D2O in place of water. Selective oxidation at sulfur in benzo[1,4,2]dithiazine 1,1-dioxide by using mCPBA as the oxidizing agent is also described.