Application of the Nickel-Mediated Neopentyl Coupling in the Total Synthesis of the Marine Natural Product Arenarol

Highly Efficient Total Synthesis of the Marine Natural Products (+)‐Avarone, (+)‐Avarol, (−)‐Neoavarone, (−)‐Neoavarol and (+)‐Aureol

“…[10] [a] 20 D = À55.2 (c = 0.07, CHCl 3 )}, in 91 % yield. Subsequent conversion of 3 to 4 was first examined using the conventional procedure (Na 2 S 2 O 4 , THF/H 2 O, RT); [25] however, the yield of the desired product 4 was moderate ( % 50 %). After several experiments, we found that the requisite conversion proceeded smoothly and cleanly by treating 3 with NaBH 4 in THF/H 2 O 10:1 at 08C for 3 min, producing the desired 4, m.p.…”

Synthetic Strategies to Terpene Quinones/Hydroquinones

“…Retrosynthetic analysis as summarized in Scheme 27 readily dissects arenarol to a neopentyl iodide 166 and 2,4-dimethoxyphenylmagnesium bromide [258]. The neopentyl iodide turn could be derived from the corresponding alcohol 167 , assuming that the hydroxyl group could be employed to control the stereochemistry of reduction at an adjacent exocyclic olefin, or the diene alcohol 169 , if the hydroxyl group could be employed to fix both adjacent stereocenters.…”

Transition Metal-Catalyzed Activation of Aliphatic C−X Bonds in Carbon−Carbon Bond Formation

“…16 This cross-coupling reaction has been used as the key step in the synthesis of the marine natural product arenarol 7 (Scheme 2). 17 The manganese complex 8 with a nontransferable ligand which can be prepared in situ has been shown to be a powerful catalyst in the cross-coupling reaction of alkyl bromides with various Grignard reagents in the presence of CuCl as a cocatalyst (Table 2). 18,19 It is highly chemoselective, and functional groups such as ketone and ester remain intact under the reaction conditions.…”