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Synthesis and Suzuki–Miyaura Cross‐Coupling of Enantioenriched Secondary Potassium β‐Trifluoroboratoamides: Catalytic, Asymmetric Conjugate Addition of Bisboronic Acid and Tetrakis(dimethylamino)diboron to α,β‐Unsaturated Carbonyl Compounds
Author(s) -
Molander Gary A.,
Wisniewski Steven R.,
HosseiniSarvari Mona
Publication year - 2013
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201300640
Subject(s) - chemistry , transmetalation , enantioselective synthesis , reagent , catalysis , potassium , yield (engineering) , conjugate , aryl , combinatorial chemistry , medicinal chemistry , enantiomer , organic chemistry , mathematical analysis , materials science , alkyl , mathematics , metallurgy
Enantioenriched potassium β‐trifluoroboratoamides have been synthesized via an asymmetric, copper‐catalyzed 1,4‐addition of tetrahydroxydiboron (BBA) and tetrakis(dimethylamino)diboron to α,β‐unsaturated amides. These dibora reagents provide access to the desired organotrifluoroborates using effective and atom economical sources of boron. The copper‐catalyzed β‐boration is extended to α,β‐unsaturated ketones and esters. The desired potassium organotrifluoroborates are synthesized with yields up to 92% and enantiomeric ratios up to 98:2. The enantioenriched potassium β‐trifluoroboratoamides are successfully cross‐coupled with an array of aryl and heteroaryl chlorides in high yield with complete stereochemical fidelity as the transmetalation proceeds through an S E 2 mechanism via an open transition state.