17376-04-4Relevant articles and documents
Laurent et al.
, p. 3423,3424 (1974)
Chiral organometallic reagents. Part XXIV.1 Iodine ate-complexes as intermediates in the iodine-lithium exchange reaction on 1,1-diiodoalkanes
Mueller, Michael,Stiasny, Hans-Christian,Broenstrup, Mark,Burton, Andrew,Hoffmann, Reinhard W.
, p. 731 - 736 (1999)
The iodine-lithium exchange reaction on the 1,1-diiodoalkanes 17 at -110 °C is initiated by the irreversible formation of yellow iodine ate-complexes, which are slowly transformed into the α-iodoalkyllithium compounds 21.
α-Iodoalkyl-iodine-ate complexes as observable intermediates in the iodine-magnesium exchange reaction
Schulze, Volker,Broenstrup, Mark,Boehm, Volker P. W.,Schwerdtfeger, Peter,Schimeczek, Michael,Hoffmann, Reinhard W.
, p. 824 - 826 (1998)
An intermediate with a half-life of 30 minutes has been observed in the iodine-magnesium exchange reaction of 1,1-diiodoalkanes in THF at -78°C. This intermediate is likely the ate complex 1. Its characteristic chemistry calls for a mechanistic reconsider
Direct Trifluoromethoxylation without OCF3-Carrier through In Situ Generation of Fluorophosgene
Donnard, Morgan,Guérin, Thomas,Hanquet, Gilles,Leroux, Frédéric R.,Panossian, Armen,Saiter, Jérémy
supporting information, p. 3139 - 3147 (2021/06/26)
Owing to the high interest in the OCF3 group for pharmaceutical and agrochemical applications, trifluoromethoxylation received great attention in the last years with several new methods for this approach towards OCF3-comprising compounds. Yet, it most often requires the beforehand preparation of specific F3CO? transfer reagents, which can be toxic, expensive, unstable, and/or generate undesired side-products upon consumption. To circumvent this, the in-situ generation of gaseous fluorophosgene from triphosgene, its conversion by fluoride into the OCF3 anion, and the direct use of the latter in nucleophilic substitutions is an appealing strategy, which, although recently approached, has not been fully exploited. We disclose herein our efforts towards this aim.
Rhodium-Catalyzed Regiodivergent Synthesis of Alkylboronates via Deoxygenative Hydroboration of Aryl Ketones: Mechanism and Origin of Selectivities
Zhang, Bing,Xu, Xin,Tao, Lei,Lin, Zhenyang,Zhao, Wanxiang
, p. 9495 - 9505 (2021/08/04)
Here, we report an efficient rhodium-catalyzed deoxygenative borylation of ketones to synthesize alkylboronates, in which the regioselectivity can be switched by the choice of the ligand. The linear alkylboronates were obtained exclusively in the presence of P(nBu)3, and PPh2Me favored the formation of branched alkylboronates. The protocol also allows access to 1,1,2-triboronates from the readily available ketones. Mechanistic studies suggest that this Rh-catalyzed deoxygenative borylation of ketones goes through an alkene intermediate, which undergoes regiodivergent hydroboration to afford linear and branched alkylboronates. The different steric effects of PPh2Me and P(nBu)3 were found to be responsible for product selectivity by density functional theory calculations. The alkene intermediate can alternatively undergo sequential dehydrogenative borylation and hydroboration to deliver the triboronates.
