A one‐pot synthesis of tetrasubstituted acrylaldehydes
Copper‐Catalyzed Synthesis of α‐Trifluoromethylacrylates from Trifluoroborylacrylates via Stereoretentive Radical Trifluoromethylation
We report the synthesis of α‐trifluoromethylacrylates from α‐trifluoroborylacrylates
- NSF-PAR ID:
- 10255382
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Synthesis & Catalysis
- Volume:
- 363
- Issue:
- 2
- ISSN:
- 1615-4150
- Page Range / eLocation ID:
- p. 425-430
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract via difunctionalization of aryl propynyl ethers has been achieved, which involves a trifluoromethylthiolation process and a radical 1,4‐aryl migration from oxygen to carbon. The reaction shows excellent conversion of aryl propynyl ethers into trifluoromethyl‐containing α,β‐unsaturated aldehydes through a radical pathway.magnified image -
more » « less
Abstract A simple one‐pot synthesis of
β ‐hydroxyallenamides is reported. This procedure entails chemo‐ and regioselective hydroboration of 3‐en‐1‐ynyl‐sulfonylamides with Cy2BH followed by homoallenylation of aldehydes to yield β‐hydroxyallenamides (up to 94% yield and >20:1 dr). Controlled synthesis of up to three continuous stereochemical elements was realized. Density functional theory (DFT) calculations suggest a concerted Zimmerman‐Traxler chair‐like transition state. Initial results suggest that enantio‐ and diastereoselective synthesis of β‐hydroxyallenamides with optically active hydroboration reagents is viable.magnified image -
more » « less
Abstract An atom‐economic approach for the synthesis of
N ‐(2‐acetoxyalkyl)isoquinolones from oxazolines and alkynes through rhodium(III)‐catalyzed auto‐tandem reactions involving C−H bond functionalization/C−N bond formation/ring opening/nucleophilic substitution is described. This protocol features high regioselectivity, tolerance of various functional groups, and retention of absolute configuration of chirality. Exploration of the reaction mechanism reveals that Cu(OAc)2not only acts as the oxidant, but also provides acetate to promote the reaction in this process.magnified image -
more » « less
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(
sp 2)−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 -
Transition Metal‐Free Aroylation of Diarylmethanes with N ‐Bn‐ N ‐Boc Arylamides and N ‐Acylpyrrolesmore » « less
Abstract In the last 20 years, efficient transition metal catalysts for the α‐arylation of enolates have been introduced. Despite the popularity and utility of these reactions, there remains room for improvement (reduced costs, elimination of transition metals and specialized ligands). Herein is reported a general, scalable and green method for aroylation of simple diarylmethane pronucleophiles through direct acyl C−N cleavage of
N ‐Bn−N ‐Boc arylamides andN ‐acylpyrroles under transition metal‐free conditions. Importantly, a 1 : 1 ratio of the amide to the pronucleophile is employed. Unlike use of Weinreb amides, this method avoids preformed organometallics (organolithium and Grignard reagents) and does not employ cryogenic temperatures, which are difficult and costly to achieve on scale. The operationally simple protocol provides straightforward access to a variety of sterically and electronically diverse 1,2,2‐triarylethanones, a group of compounds with high‐value in medicinal chemistry.magnified image
