skip to main content


Title: Mild Base Promoted Nucleophilic Substitution of Unactivated sp 3 ‐Carbon Electrophiles with Alkenylboronic Acids
Abstract

Diverse alkenylboronic acids react smoothly with varioussp3‐carbon electrophiles such as unactivated alkyl triflates in the presence of mild bases such as K3PO4. The reaction protocol is very mild and thereby enables high functional group tolerance. This transition metal‐free condition is orthogonal towards the classic transition metal catalyzed Suzuki coupling.

magnified image

 
more » « less
PAR ID:
10074391
Author(s) / Creator(s):
 ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Advanced Synthesis & Catalysis
Volume:
360
Issue:
19
ISSN:
1615-4150
Page Range / eLocation ID:
p. 3667-3671
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    With sunlight or blue LEDs irradiation, regioselective decarboxylative alkylation of various non‐aromatic heterocycles has been realized via C(sp3)‐centered radical C(sp2)−C(sp3) bond formation under oxidant‐free conditions at room temperature. This reaction readily incorporates various functional alkyl groups into heterocyclic compounds without observation of any alkyl radical rearrangement and represents a mild and general tool for the preparation of valuable alkyl group‐functionalized heterocyclic compounds.

    magnified image

     
    more » « less
  2. Abstract

    The selenenate anion (RSeO) is introduced as an active organocatalyst for the dehydrohalogen coupling of benzyl halides to formtrans‐stilbenes. It is shown that RSeOis a more reactive catalyst than the previously reported sulfur analogues (sulfenate anion, RSO) and selenolate anions (RSe) in the aforementioned reaction. This catalytic system was also applied to the benzylic‐chloromethyl‐coupling polymerization (BCCP) of a bis‐chloromethyl arene to form ppv (poly(p‐phenylene vinylene))‐type polymers with high yields, Mn(average molecular weight) up to 13,000 and Đ (dispersity) of 1.15.

    magnified image

     
    more » « less
  3. Abstract

    Aiming at the enhanced catalytic activity of fluoro‐λ3‐iodane generated from iodoarene precatalyst with Selectfluor and HF⋅pyridine, this study focused on the λ3‐iodanes bearing coordinating substituents. Compared to 4‐iodoanisole as a precatalyst of our previous method,N‐methyl‐2‐iodobenzamide or 2‐iodobenzamide worked well in the fluorocyclization ofN‐propargyl carboxamides to oxazoles. Control experiments suggest the equilibrium mixture of iodane‐amine complexes and cyclic iodane fluorides would be involved in the present catalysis.

    magnified image

     
    more » « less
  4. Abstract

    A Rh(II)/Au(I) catalyzed carbene cascade approach for the stereoselective synthesis of diverse spirocarbocycles is described. The cascade reaction involves a rhodium carbene initiatedsp2C−H functionalization followed by a gold catalyzed Conia‐ene cyclization. The cascade reaction accommodates a variety of aryl substituents as well as ring sizes and proceeds with high diastereoselectivity providing access to diverse spirocarbocycles.

    magnified image

     
    more » « less
  5. Abstract

    Benzofused lactams, especially indolin‐2‐one and dihydroquinolin‐2‐one are popular structural motives in durgs and natural products. Herein, we developed a room temperature and robust synthesis of benzofused lactams through cobalt(III)‐catalyzed C(sp2)−H amidation. In this protocol, in‐situ formation of Cp*Co(III)(ligand) catalyst from Cp*Co(CO)I2and ligand simplify the synthetic effort of cobalt complexes. Simple and readily synthesized 1,4,2‐dioxazol‐5‐ones underwent room temperature intramolecular C−H amidation and afforded a wide variety of functionalized benzofused lactams in up to 86% yield. The scalability of the reaction is also be demonstrated.

    magnified image

     
    more » « less