Hydrophosphination of CO2 with 1,3,2-Diazaphospholene (NHP-H; 1) afforded phosphorus formate (NHP-OCOH; 2) through the formation of a bond between the electrophilic phosphorus atom in 1 and the oxygen atom from CO2 , along with hydride transfer to the carbon atom of CO2 . Transfer of the formate from 2 to Ph2 SiH2 produced Ph2 Si(OCHO)2 (3) in a reaction that could be carried out in a catalytic manner by using 5 mol % of 1. These elementary reactions were applied to the metal-free catalytic N-formylation of amine derivatives with CO2 in one pot under ambient conditions.
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http://dx.doi.org/10.1002/anie.201505244 | DOI Listing |
Dalton Trans
August 2017
Department of Chemistry and Biochemistry, Mount Allison University, Sackville, NB E4L 1G8, Canada.
The transition metal-free addition of phosphinoboronate ester PhPBpin (pin = 1,2-OCMe) to heterocumulenes including carbodiimides, isocyanates, isothiocyanates and carbon dioxide has been investigated. The corresponding 1,2-addition products were readily prepared at room temperature without the need of a catalyst or added base. Addition of methanol to the compounds derived from addition of PhPBpin to carbodiimides, isocyanates, and isothiocyanates resulted in traditional hydrophosphination products.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2015
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Nanyang Link 21, Singapore 637371 (Singapore).
Hydrophosphination of CO2 with 1,3,2-Diazaphospholene (NHP-H; 1) afforded phosphorus formate (NHP-OCOH; 2) through the formation of a bond between the electrophilic phosphorus atom in 1 and the oxygen atom from CO2 , along with hydride transfer to the carbon atom of CO2 . Transfer of the formate from 2 to Ph2 SiH2 produced Ph2 Si(OCHO)2 (3) in a reaction that could be carried out in a catalytic manner by using 5 mol % of 1. These elementary reactions were applied to the metal-free catalytic N-formylation of amine derivatives with CO2 in one pot under ambient conditions.
View Article and Find Full Text PDFJ Org Chem
September 2015
Department of Chemistry, National Tsing Hua University, Hsinchu 30013, Taiwan.
Recent progress in frustrated Lewis pairs (FLPs) has attracted increasing attention. However, most of the FLPs are composed of Lewis basic phosphines and Lewis acidic boranes. In 2015, Kinjo and co-workers reported the first intramolecular boron-boron FLP, namely, 1,3,2,5-diazadiborinine (1), which showed high regioselectivity in the reactions with methyl trifluoromethansulfonate, phenylacetylene, and CO2.
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