Allylation of Unactivated and/or Functionalized Alkynes with Allylindiums

Gallium-mediated allyl transfer from bulky homoallyl alcohol to aldehydes or alkynes: Control of dynamic σ-allylgalliums based on retro-allylation reaction

“…The following compounds were characterized according to the literature: 2a [11], 2b [12], 2c [11], 2d [11], 2e [13], 2f [11], 2h [14], 2i [15], 2j [15], 2k-m [11], 2n [16], 2o [14], 2p [17], 2q [17], 6b [18], 6f [18], 6g [18], 6g-d 2 [19], 6g-d 1 [20], 6i [18], and 6n [21]. d 14.34, 15.09, 16.39, 22.89, 29.35, 29.38, 29.40, 29.50, 29.65, 32.10, 32.51, 43.88, 44.83, 76.21, 76.54, 115.86, 116.59, 130.21, 130.63, 133.57.…”

Indium in Organic Synthesis

“…96 Terminal alkynes could be similarly allylindated. [97][98][99] The intermediacy of indated species was proved by incorporation of deuterium after addition of DCl/D 2 O to the reaction mixture (Scheme 24). 98 Scheme 24 Allyl addition to terminal alkynes 98…”

Regio- and Stereoselective Allylindation of Alkynes Using InBr3 and Allylic Silanes: Synthesis, Characterization, and Application of 1,4-Dienylindiums toward Skipped Dienes

“…Carbometalation is an important synthetic method in organic synthesis because organometallic compounds are produced with an expansion of the carbon framework [ 1 , 2 , 3 , 4 , 5 , 6 , 7 ]. In particular, the allylmetalation of alkynes provides metalated skipped dienes (1,4-diene), which are effectively transformed to functionalized skipped dienes via sequential reactions [ 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 ]. Skipped diene units are present in many biologically important natural products, and are also versatile synthetic building blocks in organic synthesis [ 19 , 20 , 21 , 22 ].…”

“…In this context, we achieved regioselective anti -allylindation of simple alkynes using InBr 3 and allylic silanes ( Scheme 1 D). To the best of our knowledge, anti -allylindation of alkynes has never been established, while several syn -allylindations using allylic indiums have [ 13 , 33 , 34 , 35 , 36 , 37 , 38 , 39 ]. The 1,4-dienylindium compounds can be excellent precursors for functionalized skipped dienes due to their moderate reactivity and high compatibility with many functional groups.…”