Creating carbon–carbon bonds with samarium diiodide for the synthesis of modified amino acids and peptides

Palladium-catalyzed desulfinylative C–C allylation of Grignard reagents and enolates using allylsulfonyl chlorides and esters

“…[1][2][3][4][5][6][7][8][9][10][11] Transition metal catalyzed cross-coupling of organometallic reagents with halides or triflates constitutes today one of the most powerful methods to generate carbon-carbon bonds. [12][13][14][15][16][17] Arene-and alkanesulfonyl chlorides are inexpensive and readily available compounds.…”

(S)-4-Benzyl-2-oxazolidinone

“…179 An example of this procedure is shown in eq 96, where the chiral oxazolidinone is subjected to an acrylamide and samarium diiodide after the benzylation step providing directly the chiral ketone in 72% yield. The Evans asymmetric alkylation protocol can be extended by a direct removal of the chiral auxiliary after α-alkylation and formation of a C-C bond in on step.…”

Radicals in organic synthesis. Part 1

“…20 At first glance, this chemistry appears to permit the conjugate addition of an acyl radical equivalent 214 to an activated alkene (215) to furnish a g-keto amide 216 (Scheme 58). The transformation is quite remarkable, as decarbonylation is not a competing process; this is especially unusual for substrates, such as 214, where fragmentation would lead to a stable tertiary radical.…”

“…It has been employed in most forms of radical reactions, including ketyl-alkene couplings, conjugate additions, pinacol-like coupling reactions, deoxygenations, desulfonylations, dehalogenations and many other reduction reactions; its uses have been extensively reviewed [20][21][22] and many examples are discussed in the appropriate sections of this report.…”

“…There have been a number of specialist reviews providing comprehensive coverage of various aspects of radical chemistry published over the last five years; topics covered include free-radical cascade processes, 3 the synthesis of heterocycles by radical cyclisations, 4 the synthesis of five-and six-membered heterocycles, 5a,b 5-endo-trig cyclisations, 6 the formation of five-membered rings by translocation-cyclisation, 7 unusual radical cyclisations, 8 radical reactions in aqueous media, 9 the chemistry of ketyl radical anions formed by photoinduced electron transfer, 10 the addition of radicals to C]N bonds, 11,12 'clean' radical reagents, 13 phosphorus-based radical methodology, 14 indium and indium reagents in organic synthesis, 15a,b dichloroindane as a versatile reducing agent, 16 titanocene-mediated radical reactions, 17a,b copper(I)-catalysed atom transfer radical cyclisations, 18 atom transfer radical polymerisations (ATRP), 19a,b samarium(II) iodide in organic synthesis, [20][21][22] samarium(II) iodide in asymmetric synthesis, 23 transition metal generated radicals, 24 cerium regents in synthesis, 25 the persistent radical effect, 26a,b cyclohexa-1,4-diene-based radical reagents, 27 radical additions to aromatic systems, 28 diastereoselective radical reactions, 29a,b enantioselective radical reactions, 30-32 stereoselective conjugate additions. 33,34 radical carbonylations, 35 O-centred radicals in C-O bond formation, 36 inorganic radical reagents, 37 radical chemistry of organoboranes, 38a,b the addition of phosphorus compounds to unactivated hydrocarbons, 39 nitrogen-directed radical rearrangements, 40 thiol-mediated radical cyclisations, 41 the chemistry of N-centred radicals, 42 chirality control in photochemical reactions 43 and the carbometallation of unactivated alkenes by zinc enolate derivatives.…”