Progress in the total synthesis of inthomycins

• Bidyut Kumar Senapati

Beilstein J. Org. Chem. 2021, 17, 58–82, doi:10.3762/bjoc.17.7

• Hale and Hatakeyama [57]. Recently, Burton’s group developed some efficient and tin-free total syntheses of all three inthomycins A–C ((+)-1, (+)-2, and (−)-3) using a Suzuki or Sonogashira cross-coupling of the (E)- or (Z)-alkenyl iodides 130 with the dienylboronic ester 128 as key step (Schemes 18–22

• -catalyzed hydroboration of the terminal acetylene in 127 gave (E,E)-128 in good yield and with complete stereocontrol (Scheme 18). To accomplish the key Suzuki coupling of dienylboronic ester 128, the necessary alkenyl iodides (Z)- and (E)-130 were prepared from the propargyl alcohol (14) in good yields

• ((−)-3). Synthesis of the cross-metathesis precursors (rac)-118 and 121. Donohoe’s total synthesis of inthomycin C ((−)-3). Synthesis of dienylboronic ester (E,E)-128. Synthesis of the alkenyl iodides (Z)- and (E)-130. Burton’s total synthesis of inthomycin B ((+)-2). Burton’s total synthesis of

Copper-based fluorinated reagents for the synthesis of CF₂R-containing molecules (R ≠ F)

• Louise Ruyet and
• Tatiana Besset

Beilstein J. Org. Chem. 2020, 16, 1051–1065, doi:10.3762/bjoc.16.92

• turned out to be functional group tolerant. The same group extended their protocol to the functionalization of aryldiazonium salts [79]. Very recently, a similar protocol was applied to the pentafluoroethylation of (hetero)aryl halides as well as alkenyl iodides derived from natural compounds (e.g

CF₃SO₂X (X = Na, Cl) as reagents for trifluoromethylation, trifluoromethylsulfenyl-, -sulfinyl- and -sulfonylation. Part 1: Use of CF₃SO₂Na

• Hélène Guyon,
• Hélène Chachignon and
• Dominique Cahard

Beilstein J. Org. Chem. 2017, 13, 2764–2799, doi:10.3762/bjoc.13.272

(Z)-Selective Takai olefination of salicylaldehydes

• Stephen M. Geddis,
• Caroline E. Hagerman,
• Warren R. J. D. Galloway,
• Hannah F. Sore,
• Jonathan M. Goodman and
• David R. Spring

Beilstein J. Org. Chem. 2017, 13, 323–328, doi:10.3762/bjoc.13.35

• led to the identification of key factors responsible for this surprising inversion of selectivity, and enabled the development of a modified mechanistic model to rationalise these observations. Keywords: alkenyl iodides; salicylaldehydes; stereoselectivity; Takai olefination; transition state

Iodination of carbohydrate-derived 1,2-oxazines to enantiopure 5-iodo-3,6-dihydro-2H-1,2-oxazines and subsequent palladium-catalyzed cross-coupling reactions

• Michal Medvecký,
• Igor Linder,
• Luise Schefzig,
• Hans-Ulrich Reissig and
• Reinhold Zimmer

Beilstein J. Org. Chem. 2016, 12, 2898–2905, doi:10.3762/bjoc.12.289

• the enol ether unit of 3,6-dihydro-2H-1,2-oxazines 3 can efficiently be converted into the corresponding 5-iodo-substituted compounds 4 under mild reaction conditions using molecular iodine in the presence of pyridine as base. The obtained alkenyl iodides 4 are ideal candidates for further

Weakly nucleophilic potassium aryltrifluoroborates in palladium-catalyzed Suzuki–Miyaura reactions: relative reactivity of K[4-RC₆F₄BF₃] and the role of silver-assistance in acceleration of transmetallation

• Vadim V. Bardin,
• Anton Yu. Shabalin and
• Nicolay Yu. Adonin

Beilstein J. Org. Chem. 2015, 11, 608–616, doi:10.3762/bjoc.11.68

• reported by Kishi et al. [16] for the cross-coupling of alkenylboronic acids with alkenyl iodides in the presence of Ag2O and elucidated by formation of AgOH which acts like aqueous KOH or TlOH. Korenaga et al. [20] have studied Pd-catalyzed cross-coupling of C6F5B(OH)2 with aryl halides in the presence of