General and selective syn-carboxylation-trifluoromethylation of terminal alkynes: application to the late-stage modification of dehydrocholic acid

2019 ◽  
Vol 55 (28) ◽  
pp. 4099-4102 ◽  
Author(s):  
Song-Lin Zhang ◽  
Chang Xiao ◽  
Hai-Xing Wan ◽  
Xiaoming Zhang
Keyword(s):  
Late Stage ◽  
Triple Bond ◽  
Biologically Active ◽  
Terminal Alkynes ◽  
Dehydrocholic Acid ◽  
Enol Esters

A general and selective syn-carboxylation-trifluoromethylation across the triple bond of terminal alkynes is developed by virtue of a reactive Cu(iii)–CF3 complex, which produces a broad range of biologically active trifluoromethylated enol esters with excellent regio- and stereoselectivity.

Controllable assembly of the benzothiazole framework using a CC triple bond as a one-carbon synthon

2018 ◽  
Vol 54 (14) ◽  
pp. 1742-1745 ◽  
Author(s):  
Yubing Huang ◽  
Donghao Yan ◽  
Xu Wang ◽  
Peiqi Zhou ◽  
Wanqing Wu ◽  
...  
Keyword(s):  
Triple Bond ◽  
Elemental Sulfur ◽  
Terminal Alkynes ◽  
One Pot ◽  
Benzothiazole Derivatives

A one-pot protocol to controllably assemble diverse benzothiazole derivatives from o-haloanilines, elemental sulfur and terminal alkynes has been realized.

scholarly journals Modular synthesis of α-fluorinated arylmethanes via desulfonylative cross-coupling

2019 ◽  
Vol 10 (1) ◽  
Author(s):  
Masakazu Nambo ◽  
Jacky C.-H. Yim ◽  
Luiza B. O. Freitas ◽  
Yasuyo Tahara ◽  
Zachary T. Ariki ◽  
...  
Keyword(s):  
Biological Activity ◽  
Late Stage ◽  
Recent Progress ◽  
Cross Coupling ◽  
Biologically Active Compounds ◽  
Biologically Active ◽  
Active Compounds ◽  
Arylboronic Acids ◽  
Modular Synthesis ◽  
Synthetic Routes

Abstract α-Fluoromethylarenes are common substructures in pharmaceuticals and agrochemicals, with the introduction of fluorine often resulting in improved biological activity and stability. Despite recent progress, synthetic routes to α-fluorinated diarylmethanes are still rare. Herein we describe the Pd-catalyzed Suzuki-Miyaura cross-coupling of α-fluorinated benzylic triflones with arylboronic acids affording structurally diverse α-fluorinated diarylmethanes. The ease of synthesis of fluorinated triflones as the key starting materials enables powerful late-stage transformations of known biologically active compounds into fluorinated analogs.

Synthetic approaches to [5,6]-benzannulated spiroketal natural products

2011 ◽  
Vol 84 (6) ◽  
pp. 1379-1390 ◽  
Author(s):  
Michael C. McLeod ◽  
Margaret A. Brimble ◽  
Dominea C. K. Rathwell ◽  
Zoe E. Wilson ◽  
Tsz-Ying Yuen
Keyword(s):  
Natural Products ◽  
Total Synthesis ◽  
Electronic Properties ◽  
Late Stage ◽  
Biologically Active ◽  
Formal Synthesis ◽  
Berkelic Acid ◽  
Synthetic Approaches

Studies toward the synthesis of three biologically active [5,6]-benzannulated spiroketal natural products are described. The first total synthesis of paecilospirone is reported, employing a late-stage, pH-neutral spiroketalization. A formal synthesis of γ-rubromycin is described, where the spiroketal moiety is formed by delicate manipulation of the electronic properties of the spirocyclization precursor. Finally, model work toward the total synthesis of berkelic acid is summarized, introducing a novel Horner–Wadsworth–Emmons/oxa-Michael (HWE/oxa-M) cascade to access the spiroketal precursor.

scholarly journals Late-Stage Diversification of Biologically Active Molecules via Chemoenzymatic C–H Functionalization

ACS Catalysis ◽  
2016 ◽  
Vol 6 (3) ◽  
pp. 1451-1454 ◽  
Author(s):  
Landon J. Durak ◽  
James T. Payne ◽  
Jared C. Lewis
Keyword(s):  
Late Stage ◽  
Biologically Active

scholarly journals Photooxygenation of an amino-thienopyridone yields a more potent PTP4A3 inhibitor

2016 ◽  
Vol 14 (27) ◽  
pp. 6398-6402 ◽  
Author(s):  
Joseph M. Salamoun ◽  
Kelley E. McQueeney ◽  
Kalyani Patil ◽  
Steven J. Geib ◽  
Elizabeth R. Sharlow ◽  
...  
Keyword(s):  
Late Stage ◽  
Biologically Active

Late-stage photooxygenation can generate novel biologically active lead structures.

scholarly journals Co-Catalyzed E-(β)-Selective Hydrogermylation of Terminal Alkynes

2021 ◽  
Author(s):  
Maxim Radzhabov ◽  
Neal Mankad
Keyword(s):  
Natural Products ◽  
Late Stage ◽  
Functional Group ◽  
Terminal Alkynes ◽  
Mechanistic Studies ◽  
Practical Utility ◽  
Π Complex ◽  
Accessible Method ◽  
High Yields

<a></a><a>We demonstrated unprecedentedly that Co complexes can catalyze hydrogermylation of alkynes. Subsequently, a selective, accessible method was developed to synthesize E-(β)-vinyl(trialkyl)germanes from various terminal alkynes with high yields. As shown on multiple examples, the developed method demonstrates broad functional group tolerance and practical utility for late-stage hydrogermylation of drugs and natural products. The method is compatible with alkynes bearing both aryl and alkyl substituents, providing unrivaled selectivity for previously challenging 1° alkyl-substituted alkynes. Moreover, the catalyst used in this method, Co<sub>2</sub>(CO)<sub>8</sub>, is a cheap and commercially available reagent. Conducted mechanistic studies supported syn-addition of Bu<sub>3</sub>GeH to an alkyne</a> π-complex.

Undirected, Selective Csp2-H Alkynylation of Five-membered Heteroarenes

2021 ◽  
Vol 25 ◽  
Author(s):  
Fabio Bellina ◽  
Martina La Manna ◽  
Elisabetta Rosadoni
Keyword(s):  
Late Stage ◽  
Structural Characteristics ◽  
Terminal Alkynes ◽  
Carbon Bond ◽  
Carbon Carbon Bond

: The functionalization of Csp2-H bond of heteroarene with an alkyne represents one of the most attractive procedures for the late-stage functionalization of the aromatic core due to the structural characteristics and synthetic versatility given by a triple carbon-carbon bond. The aim of this review is to cover the most significant results reported in the literature regarding the synthesis of alkynyl-substituted five-membered heteroarenes by selective direct Csp2-H alkynylation with 1-haloalkynes and analogs, or by cross-dehydrogenative alkynylation (CDA) with terminal alkynes, without making use of directing groups.

Recent Advances in the Transition Metal Catalyzed Addition of Carboxylic Acids to Alkynes

2021 ◽  
Vol 25 ◽  
Author(s):  
Victorio Cadierno
Keyword(s):  
Natural Products ◽  
Transition Metal ◽  
Carboxylic Acids ◽  
Heterocyclic Compounds ◽  
Biologically Active ◽  
Recent Advances ◽  
Enol Esters ◽  
Cascade Processes ◽  
Transition Metal Catalyzed ◽  
Metal Catalyzed

: Recent advances in the metal-catalyzed hydrofunctionalization of alkynes with carboxylic acids are comprehensively reviewed. Both inter- and intramolecular processes, leading respectively to enol esters and lactones, are discussed, as well as the involvement of these transformations in the synthesis of natural products and biologically active molecules, and the assembly of elaborated heterocyclic compounds though cascade processes. Literature published since 2011 is covered.

Sign in / Sign up

Export Citation Format

Share Document