Synthesis of indolocarbazoles was achieved through thermal electrocyclization followed by triethyl phosphite‐mediated nitrene insertion reactions. Total synthesis of staurosporinone analogues was achieved from commercially available 2‐methylindole. The CDK5/p25 kinase inhibition potential of some representative staurosporinone analogues was explored by using the TRFRET kinase assay.

The FeCl3/DDQ‐PTSA/NBS‐mediated cyclization (DDQ = 2,3‐dichoro‐5,6‐dicyano‐1,4‐benzoquinone, PTSA = p‐toluenesulfonic acid, NBS = N‐bromosuccinimide) of 2‐arylvinyl‐3‐indolylpyrrole led to the formation of the pyrrolo[2,3‐c]carbazole core unit of dictyodendrins in yields of 75–90 %. The cyclization method was also successfully applied to the syntheses of pyrrolodibenzothiophene and benzo[e]indole derivatives.

A facile preparation of trans‐epoxides was achieved by a (EtO)3P–ZnBr2‐mediated deoxygenation reaction of the corresponding 2‐nitrobenzaldehydes. The sterically hindered analogues of 2‐nitrobenzaldehyde underwent a reaction with triethyl phosphite in the presence of ZnBr2 as the catalyst to form benzisoxazoles as the sole product. Under identical conditions, the reactions of electron‐rich as well as moderately electron‐deficient aryl aldehydes furnished the corresponding α‐hydroxy phosphonate esters.

A straightforward and general method for the synthesis of annulated thiophene, dibenzothiophene, and carbazoles analogues has been achieved involving alkylation of 2-bromo-1-(phenylsulfonylmethyl)arene/heteroarene with arylmethyl bromides/heteroarylmethyl bromides using t-BuOK as a base in DMF, followed by Pd(0)-mediated intramolecular Heck coupling in the presence of KCO in DMF at 80-140 °C. The attractive feature of this protocol is that a wide variety of π-conjugated heterocycles could be readily accessed by an appropriate choice of arylmethylsulfones and benzylic bromides.

One-pot synthesis of 3,4-benzo[c]-β-carbolines was achieved from 2-aryl(tosylamino)methyl-3-bromoindoles via 10 mol % Pd(OAc) 2 /PPh 3 -mediated intramolecular Heck coupling using K 2 CO 3 as a base in DMF at 110 °C with concomitant aromatization through an elimination of tosylsulfinic acid. Under identical conditions, the isomeric 3-aryl(tosylamino)methyl-2bromoindoles upon intramolecular Heck reaction furnished benzo [4,5]isothiazolo[2,3-a]indole 5,5-dioxides instead of the expected γ-carbolines. However, synthesis of the expected γcarboline framework, 3-tosyl-6,9-dihydro-1,2-benzo[a]-γ-carbolines, could be achieved from 3-aryl(tosylamino)methyl-2bromoindoles containing a mesitylene sulfonyl unit as a protecting group on the indole nitrogen.