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
Two-Step Protocol for Iodotrimethylsilane-Mediated Deoxy-Functionalization of Alcohols
Chen, Yuming,He, Ru,Song, Hongjian,Yu, Guoqing,Li, Chenglin,Liu, Yuxiu,Wang, Qingmin
supporting information, p. 1179 - 1183 (2021/02/01)
We have developed a two-step protocol for iodotrimethylsilane-mediated deoxy-functionalization of primary and secondary alcohols to afford products containing a C?N, C?S, or C?O bond. In the first step the alcohol undergoes iodination with iodotrimethylsilane, and in the second, the iodine atom is replaced by a N, S, or O nucleophile. Compared with traditional Mitsunobu reaction, non-acidic pre-nucleophiles can be used, and the reaction proceeds with retention of configuration. This operationally simple, highly efficient protocol can be used for some natural products and small-molecule drugs containing hydroxy-group.
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.