The association of the ferrous complex FeCl(dmpe) () with alkali bases M(hmds) (M = Li, Na, K) proves to be an efficient platform for the activation of Ar-H bonds. Two mechanisms can be observed, leading to either Ar-Fe species by deprotonative ferration or hydrido species Ar-Fe-H by oxidative addition of transient Fe(dmpe) generated by reduction of . Importantly, the nature of the alkali cation in M(hmds) has a strong influence on the preferred path. Starting from the same iron precursor, diverse catalytic applications can be explored by a simple modulation of the M cation. Possible strategies enabling cross-coupling using arenes as pro-nucleophiles, reductive dehydrocoupling, or deuteration of B-H bonds are discussed.
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http://dx.doi.org/10.1021/jacsau.3c00649 | DOI Listing |
JACS Au
February 2024
CNRS, Institute of Chemistry for Life and Health Sciences, CSB2D, Chimie ParisTech, PSL University, 75005 Paris, France.
The association of the ferrous complex FeCl(dmpe) () with alkali bases M(hmds) (M = Li, Na, K) proves to be an efficient platform for the activation of Ar-H bonds. Two mechanisms can be observed, leading to either Ar-Fe species by deprotonative ferration or hydrido species Ar-Fe-H by oxidative addition of transient Fe(dmpe) generated by reduction of . Importantly, the nature of the alkali cation in M(hmds) has a strong influence on the preferred path.
View Article and Find Full Text PDFJ Am Chem Soc
January 2023
State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, China.
A unified strategy toward asymmetric divergent syntheses of nine C8-ethano-bridged diterpenoids (candol A, powerol, sicanadiol, -candol A, atisirene, -atisan-16α-ol, 4-decarboxy-4-methyl-GA, trachinol, and -beyerane) has been developed based on late-stage transformations of common synthons having -kaurane and -trachylobane cores. The expeditious assembly of crucial advanced -kaurane- and -trachylobane-type building blocks is strategically explored through a regioselective and diastereoselective Fe-mediated hydrogen atom transfer (HAT) 6--trig cyclization of the alkene/enone and 3--trig cyclization of the alkene/ketone, showing the multi-reactivity of densely functionalized polycyclic substrates with π and π systems in HAT-initiated reactions. Following the rapid construction of five major structural skeletons (-kaurane-, -atisane-, -beyerane-, -trachylobane-, and -gibberellane-type), nine C8-ethano-bridged diterpenoids could be accessed in the longest linear 8 to 11 steps starting from readily available chiral γ-cyclogeraniol and known chiral γ-substituted cyclohexenone , in which enantioselective total syntheses of candol A (, 8 steps), powerol (, 9 steps), sicanadiol (, 10 steps), -candol A (, 8 steps), -atisan-16α-ol (, 11 steps), and trachinol (, 10 steps) are achieved for the first time.
View Article and Find Full Text PDFJ Org Chem
December 2020
Department of Chemistry and the Skaggs Institute for Chemical Biology, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, United States.
Herein, the first total syntheses of (-)-pseudocopsinine () and (-)-minovincine () from a common intermediate are detailed, enlisting late-stage, hydrogen atom transfer (HAT)-mediated free radical bond formations (C20-C2 and C20-OH, respectively) that are unique to their core or structure. The approach to features an Fe-mediated HAT reaction of the intermediate olefin , effecting a transannular C20-C2 free radical cyclization of a challenging substrate with formation of a strained [2.2.
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