6279-35-2Relevant academic research and scientific papers
Cobalt Catalyst Determines Regioselectivity in Ring Opening of Epoxides with Aryl Halides
Potrz?saj, Aleksandra,Musiejuk, Mateusz,Cha?adaj, Wojciech,Giedyk, Maciej,Gryko, Dorota
supporting information, p. 9368 - 9376 (2021/06/28)
Ring-opening of epoxides furnishing either linear or branched products belongs to the group of classic transformations in organic synthesis. However, the regioselective cross-electrophile coupling of aryl epoxides with aryl halides still represents a key challenge. Herein, we report that the vitamin B12/Ni dual-catalytic system allows for the selective synthesis of linear products under blue-light irradiation, thus complementing methodologies that give access to branched alcohols. Experimental and theoretical studies corroborate the proposed mechanism involving alkylcobalamin as an intermediate in this reaction.
Regioselectivity of the rhodium-catalyzed hydroboration of vinyl arenes: Electronic twists and mechanistic shifts
Edwards, David R.,Hleba, Yonek B.,Lata, Christopher J.,Calhoun, Larry A.,Crudden, Cathleen M.
, p. 7799 - 7802 (2008/09/18)
Any substituent does it: The hydroboration of vinyl arenes with pinacol borane (HBPin) and cationic rhodium complexes selectively placed the boron proximal to the aryl rather than phenyl ring, regardless of whether this ring bears electron-donating or electron-withdrawing substituents. In competition experiments between styrene and various vinyl arenes, preferential hydroboration also occured at the substituted arene (see scheme). Hammett plots indicate a break in the mechanism. (Chemical Equation Presented).
Direct preparation of benzylic manganese reagents from benzyl halides, sulfonates, and phosphates and their reactions: Applications in organic synthesis
Suh, YoungSung,Lee, Jun-Sik,Kim, Seoung-Hoi,Rieke, Reuben D.
, p. 20 - 36 (2007/10/03)
The use of highly active manganese (Mn)*, prepared by the Rieke method, was investigated for the direct preparation of benzylic manganese reagents. The oxidative addition of the highly active manganese to benzylic halides was easily completed under mild conditions. Moreover, benzylic manganese sulfonates and phosphates were prepared by direct oxidative addition of Mn* to the carbon-oxygen bonds of benzylic sulfonates and phosphates. The resulting benzylic manganese reagents were found to undergo cross-coupling reactions with a variety of electrophiles. Most of these reactions were carried out in the absence of any transition metal catalyst under mild conditions. In addition, the use of highly active manganese was also studied for preparation of homo-coupled products of functionalized benzyl halides without transition metal catalysts. These useful approaches provided not only a facile synthetic route to the preparation of resoricinolic lipids but a facile synthesis of functionalized 4-benzylpyridines by regioselective and chemo selective γ-addition of benzylic group to N-alkoxycarbonylpyridinum salts.
Benzylic Manganese Halides, Sulfonates, and Phosphates: Preparation, Coupling Reactions, and Applications in Organic Synthesis
Kim, Seung-Hoi,Rieke, Reuben D.
, p. 2322 - 2330 (2007/10/03)
The use of highly active manganese, prepared by the Rieke method, for the direct preparation of benzylic manganese reagents was investigated. The oxidative addition of the highly active manganese (Mn*) to benzylic halides was easily completed under mild conditions. More importantly, benzylic manganese sulfonates and phosphates were prepared by direct oxidative addition of Mn* to the carbon-oxygen bonds of benzylic sulfonates and phosphates. The resulting benzylic manganese reagents were found to undergo cross-coupling reactions with a variety of electrophiles. The majority of these reactions were carried out in the absence of any transition metal catalyst under mild conditions. This approach also provided a facile synthetic route to the preparation of resorcinolic lipids.
A new synthetic protocol for the direct preparation of organomanganese reagents; organomanganese tosylates and mesylates
Kim, Seung-Hoi,Rieke, Reuben D.
, p. 4931 - 4934 (2007/10/03)
A new synthetic route to organomanganese sulfonate reagents has been developed. These useful reagents can be readily prepared via direct oxidative addition of highly reactive manganese to carbon-oxygen bonds of the corresponding tosylates and mesylates under mild conditions.
NOVEL SYNTHESIS OF BENZYLLITHIUMS FROM BENZYLSELENIDES
Clarembeau, M.,Krief, A.
, p. 1093 - 1096 (2007/10/02)
Benzylselenides are found to be valuable precursors of benzyllithiums.The scope of the new method is disclosed.
