Total Syntheses of (R)-Strongylodiols C and D

Abstract

The first total syntheses of two marine natural products, (R)-strongylodiols C and D, with 99% ee were achieved. The key steps of the strategy include the zipper reaction of an alkyne, the asymmetric alkynylation of an unsaturated aliphatic aldehyde catalyzed with Trost's ProPhenol ligand, and the Cadiot-Chodkiewicz cross-coupling reaction of a chiral propargylic alcohol with a bromoalkyne.

Total Synthesis and Structural Elucidation of Two Unusual Non‐Methylene‐Interrupted Fatty Acids in Ovaries of the Limpet Cellana toreuma

“…Therefore, the main task for the synthesis of 22 should be concentrated in the preparation of fragment C′ and the subsequent coupling of fragment A and C′. Lindlar hydrogenation of product 40 was carried out in a similar way to the cases of preparation of 10-undecyn-1-ol to give 12-tridecen-1-ol (41) in 93% yield, and 40 was then treated with CBr 4 and Ph 3 P to afford 42 in quantitative yield (Scheme 6). [Procedure: (a) NaH (5.2 eq.…”

“…However, this method is applicable only to the synthesis of 1,5-dienic structure and is not suitable for the synthesis for our purpose of fatty acids 20-23 having remote dienic structures. Previously, alkynezipper reaction was often applied to the synthesis of a variety of fatty acids and their derivatives as the key step of preparation of their carbon chains [37][38][39][40][41][42], and these successful results also led us to envision attempts for the synthesis of our target compounds by using the synthetic pathway involving the alkyne-zipper reaction. The retrosynthetic analysis of the target fatty acids in this research work is outlined in Scheme 3, and, especially, both fragment A and fragment B could be synthetized from the common starting compound, i.e., 2-propyn-1-ol [propargyl alcohol (24)], through a similar procedure involving alkylation, isomerization of the internal C-C triple bonds of intermediates D and E into the terminal position by using the alkyne-zipper reaction [36].…”

Current Applications of Suzuki–Miyaura Coupling Reaction in The Total Synthesis of Natural Products: An update

“…In 2007, Liu and co-workers separated four new lamellarin-like phenolic pyrroles, Neolamellarin A 382 from sponge Dendrilla nigra. [205] Recently, a concise total synthesis of five permethylated derivatives of Neolamellarin A 382 were achieved in five steps and reported. For this purose, 3,4-diiodinated pyrrole 383 was synthesized through diiodination of (TIPS)substituted derivative.…”

“…During this period, SMCR has been practically employed in a plethora of total synthesis of diverse natural products as a key step (steps). Some examples are the total synthesis of (-)-Stegane [140] , Phidianidines [188] , Bongkrekic acid [205] , Thailanstatin A, [215] Virgatolides B, [222] Ripostatins, [223] (-)-Ecklonialactone B, [225] Paracaseolide A, [88] Dihydrocodeine, [86] Hirtellanine A. [79] In summary, the structural diversity of the naturally occurring compounds pronounced in this review demonstrates the versatility of SMCR should attract the attentions of organic synthetic chemists and encourage them to focus on the applications of this reaction towards the chemistry of natural products with less limitation, compared with the other relevant reactions for C-C bond formations.…”

Arylation of Azaarylmethylamines with Aryl Chlorides and a NiBr2/NIXANTPHOS‐based Catalyst

“…[1] They have attracted significant attention due to their diverse activity against tumors, [2] viruses, [3] HIV, [4] tuberculosis, [5] iron metabolic disorders, [6] and cortisol dependent diseases. [7] Some prominent examples of aryl(azaaryl)methylamines are illustrated in Figure 1. Classic approaches to the synthesis of aryl(azaaryl)methylamines include addition of organometallic reagents to aldimines, [8] ketimine reduction [9] and C–N coupling reactions.…”