Amine, enamine/imine, or enamide moieties, as are accessible by hydroamination or -amidation reactions, are widely encountered in the scaffolds of natural products or synthetic drugs (Figure 1). Monomorine is one of the first natural products that became accessible by a synthetic sequence involving a hydroamination step. 2

While the synthesis of biaryls has advanced rapidly in the past decades, cross-Ullman couplings of aryl chlorides, the most abundant aryl electrophiles, have remained elusive. Reported here is the first general cross-Ullman coupling of aryl chlorides with aryl triflates. The selectivity challenge associated with coupling an inert electrophile with a reactive one is overcome using a multimetallic strategy with the appropriate choice of additive. Studies demonstrate that LiCl is essential for effective cross-coupling by accelerating the reduction of Ni(II) to Ni(0) and counteracting autoinhibition of reduction at Zn(0) by Zn(II) salts. The modified conditions tolerate a variety of functional groups on either coupling partner (42 examples), and examples include a three-step synthesis of flurbiprofen.

Sulfone derivatives are important synthetic intermediates. However, the general method for their preparation is through traditional coupling reaction: the alkylation of sodium sulfinates with phenacyl halides. Based on our previous work on sodium sulfinates and oxime acetates, we herein report a novel method for sulfone derivatives by oxidative coupling with sodium sulfinates and oxime acetates using copper as catalyst. The sulfonylvinylamine products could be formed in excellent yields. Upon hydrolysis by silica gel in CH2 Cl2 , β-ketosulfones could also be efficiently constructed. Various sulfonylvinylamines and β-ketosulfones were obtained in good to excellent yields under the optimized reaction conditions. Mechanistic studies indicated that this transformation involved copper-catalyzed N-O bond cleavage, activation of a vinyl sp(2) C-H bond, and C-S bond formation. The oxime acetates act as both a substrate and an oxidant, thus the reaction needs no additional oxidants or additives.

A new and convenient method for the construction of sulfonamides via a copper-catalyzed oxidative coupling between sodium sulfinates and amines with 1 atm O2 or DMSO as the oxidant was described. This method provides efficient and robust synthesis of functional sulfonamides in good yields and excellent chemoselectivity. And detailed mechanistic studies showed that this transformation may go through a single electron transfer (SET) pathway.

The fifth-order two-dimensional (2D) Raman spectrum of liquid formamide has been obtained. The absolute signal levels, qualitative features, as well as quantitative aspects of the 2D spectrum are found to be in good agreement with recent molecular dynamics calculations. The most important singular feature is the relatively strong rephasing signal observed along the diagonal. This finding illustrates the more structured nature of the hydrogen bond network of liquid formamide in comparison with simple liquids as exemplified by CS(2). The theoretical calculations have been extended to include comparisons of different potentials that illustrate the sensitivity of the experiment to the anharmonic motions in the liquid state. The theoretical results point out the key features in the 2D spectrum that probe the essential details in the intermolecular potential. The experiment has been demonstrated to provide new insight into collective effects operating in hydrogen bonded liquids and opens up the exploration of other liquids with this approach.