The fluoride-assisted ethynylation of ketones and aldehydes is described using commercially available calcium carbide with typically 5 mol % of TBAF·3H2O as the catalyst in DMSO. Activation of calcium carbide by fluoride is thought to generate an acetylide "ate"-complex that readily adds to carbonyl groups. Aliphatic aldehydes and ketones generally provide high yields, whereas aromatic carbonyls afford propargylic alcohols with moderate to good yields. The use of calcium carbide as a safe acetylide ion source along with economic amounts of TBAF·3H2O make this procedure a cheap and operationally simple method for the preparation of propargylic alcohols.

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An efficient and inexpensive synthesis of diaryl ethers has been developed. The process involves the nucleophilic aromatic substitution of electron‐deficient aryl halides and phenols and is mediated by potassium fluoride/Clinoptilolite (KF/CP) in dimethyl sulfoxide (DMSO). The approach affords good to excellent yields of the arylated products without the need for additional cation capture. The solid base is also efficient in the Ullmann ether synthesis.

A new Kinugasa reaction protocol has been elaborated for the one-pot synthesis of 4-substituted β-lactams utilizing calcium carbide and nitrone derivatives. Calcium carbide is thereby activated by TBAF·3H2O in the presence of CuCl/NMI. The ease of synthesis and use of inexpensive chemicals provides rapid access of practical quantities of β-lactams exclusively substituted at position 4.

We present the controlled monochlorination of aliphatic and benzylic hydrocarbons with only 1 equiv of substrate at 25-30 °C using N-hydroxyphthalimide (NHPI) as radical initiator and commercially available trichloroisocyanuric acid (TCCA) as the chlorine source. Catalytic amounts of CBr reduced the reaction times considerably due to the formation of chain-carrying ·CBr radicals. Benzylic C-H chlorination affords moderate to good yields for arenes carrying electron-withdrawing (50-85%) or weakly electron-donating groups (31-73%); cyclic aliphatic substrates provide low yields (24-38%). The products could be synthesized on a gram scale followed by simple purification via distillation. We report the first direct side-chain chlorination of 3-methylbenzoate affording methyl 3-(chloromethyl)benzoate, which is an important building block for the synthesis of vasodilator taprostene.