- Iron-Catalyzed Tertiary Alkylation of Terminal Alkynes with 1,3-Diesters via a Functionalized Alkyl Radical
-
Direct oxidative C(sp)?H/C(sp3)?H cross-coupling offers an ideal and environmentally benign protocol for C(sp)?C(sp3) bond formations. As such, reactivity and site-selectivity with respect to C(sp3)?H bond cleavage have remained a persistent challenge. Herein is reported a simple method for iron-catalyzed/silver-mediated tertiary alkylation of terminal alkynes with readily available and versatile 1,3-dicarbonyl compounds. The reaction is suitable for an array of substrates and proceeds in a highly selective manner even employing alkanes containing other tertiary, benzylic, and C(sp3)?H bonds alpha to heteroatoms. Elaboration of the products enables the synthesis of a series of versatile building blocks. Control experiments implicate the in situ generation of a tertiary carbon-centered radical species.
- Tian, Ming-Qing,Shen, Zhen-Yao,Zhao, Xuefei,Walsh, Patrick J.,Hu, Xu-Hong
-
supporting information
p. 9706 - 9711
(2021/03/19)
-
- Divergent C-H Oxidative Radical Functionalization of Olefins to Install Tertiary Alkyl Motifs Enabled by Copper Catalysis
-
An efficient tertiary alkylation reaction of olefins with 1,3-dicarbonyl compounds was developed by virtue of copper catalyst without the use of expensive ligands or additives. In contrast to alkyl Heck-type reaction, alkyl halide is not required. Notably
- Tian, Ming-Qing,Wang, Cong,Hu, Xu-Hong,Loh, Teck-Peng
-
supporting information
p. 1607 - 1611
(2019/03/07)
-
- POLYVALENT ESTER COMPOUND AND METHOD FOR PRODUCING THE SAME
-
PROBLEM TO BE SOLVED: To provide a polyvalent ester compound which has high compatibility with an acrylic resin, can improve bending resistance when used in an acrylic resin film, is excellent in handleability, has less bleed-out, is environment-friendly because of nonvolatile or low volatile, and can be used as a plasticizer. SOLUTION: There is provided a polyvalent ester compound being a polyvalent ester compound having an atomic group (A) having at least two ester groups and at least one connection portion and a connection part (B), where the polyvalent ester compound has at least two atomic groups (A), the atomic group (A) is bonded to other atomic groups (A) through the connection part (B), the atomic groups (A) may be the same or different, and the connection part (B) is a polyvalent ester compound being a bivalent or more group having at least one carbon atom. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
- -
-
Paragraph 0072
(2017/09/14)
-
- Octacidomycins, III: Synthetic Structural Analogues from C5-Units
-
The total synthesis of an isoprenoid-like analogue (2) of octacidomycin (1), a novel oligocarboxylic acid antibiotic, is described.Starting from 3 (Scheme 1) and the tetraethylester of 1,11-dibromoundecane-4,4,8,8-tetracarboxylic acid (6) as a key compound systematical fragment condensations lead to the pepntadecacarboxylic acid 12 and hence to the 1,3,7,11,15,19,23,27-heptacosane-octacarboxylic acid 2.This contains regularly connected C5- instead of C7-units and shows contracted distances between the acid groups.The newly developed synthesis yields a hitherto unknown type of oligocarboxylic acids and some useful intermediates with one or two terminal vinylic functions (13-15). - Keywords: Antibiotics, Octacidomycins, Oligocarboxylic Acids, Synthesis
- Krause, Andreas,Lackner, Helmut
-
p. 1550 - 1556
(2007/10/03)
-
- SYNTHESIS OF POLYFUNCTIONAL ALIPHATIC CARBONYL COMPOUNDS UNDER PHASE-TRANSFER CONDITIONS
-
We have studied mono- and dialkylation of malonic, acetoacetic, and cyanoacetic esters with esters of haloacetic and β-halopropionic acids and addition of the CH acids mentioned and their analogues to methyl and ethyl acrylate under phase-transfer catalysis conditions, and also deethoxycarbonylation of the obtained products.We have demonstrated for the first time the possibility of Dieckmann cyclization under phase-transfer catalysis conditions and have developed a simple method for the synthesis of 2,3-di(ethoxycarbonyl)cyclopentanone, a key intermediate in the synthesis of deoxyprostaglandins, by cyclization of triethyl 1,2,4-butanetricarboxylate.
- Sizov, A. Yu.,Dombrovskii, V. A.,Yanovskaya, L. A.
-
p. 955 - 961
(2007/10/02)
-
- NUCLEOPHILIC RING OPENING OF DIETHYL 1,1-CYCLOPROPANEDICARBOXYLATE USING Na2Fe(CO)4*3/2 DIOXANE
-
Diethyl 1,1-cyclopropanedicarboxylate undergoes nucleophilic ring opening with Na2Fe(CO)4*3/2 dioxane under CO at room temperature to produce a variety of carbonylated products.
- Tamblyn, William H.,Waltermire, Robert E.
-
p. 2803 - 2806
(2007/10/02)
-
- One-Pot Synthesis of cis Fixed β-Diketones of Bicycloalkanes, 2
-
Starting from 2-cycloalken-1-ones 1 the substituted cis fixed β-diketones of bicycloalkanes 4 have been obtained by a combined Michael addition of α,α,ω-alkanetricarboxylates (and related species) 2 and Dieckmann cyclization of the intermediates 3.Reactions of the β-diketone system as well as modifications of the disubstituted malonate system of 4 are reported.
- Schank, Kurt,Lorig, Werner
-
p. 112 - 136
(2007/10/02)
-