132532-04-8Relevant articles and documents
Enantioselective conjugate addition of diethylzinc to acyclic enones using a copper phosphino-phenol complex as catalyst
Ito, Katsuji,Eno, Shuuichiro,Saito, Bunnai,Katsuki, Tsutomu
, p. 3981 - 3985 (2005)
Newly designed phosphino-phenol 1c was found to be an efficient chiral auxiliary for copper-mediated asymmetric conjugate addition of diethylzinc to acyclic enones. High enantioselectivity up to >99% ee was achieved in the reaction of acyclic α,β-enones.
A new class of 3′-sulfonyl binaphos ligands: Modulation of activity and selectivity in asymmetric palladium-catalysed hydrophosphorylation of styrene
Barta, Katalin,Francio, Giancarlo,Leitner, Walter,Lloyd-Jones, Guy C.,Shepperson, Ian R.
, p. 2013 - 2023 (2008)
Palladium-catalysed monophosphorylation of (R)-2,2′- bisperfluoroalkanesulfonates of BINOL (RF = CF3 or C 4F9) by a diaryl phosphinate [Ar2P(O)H] followed by phosphine oxide reduction (Cl3SiH) then lithium diisopropylamide-mediated anionic thia-Fries rearrangement furnishes enantiomerically-pure (R)-2′-diarylphosphino-2′-hydroxy-3′- perfluoralkanesulfonyl-1,1′-binaphthalenes [(R)-8ab and (R)-8g-j], which can be further diversified by Grignard reagent (RMgX)-mediated CF 3-displacement [→(R)-8c-f]. Coupling of (R)-8a-j with (S)-1,1′-binaphthalene-2,2′-dioxychlorophosphine (S)-9 generates 3′-sulfonyl BINAPHOS ligands (R,S)-10a-j in good yields (43-82%). These new ligands are of utlility in the asymmetric hydrophosphonylation of styrene (1) by 4,4,5,5-tetramethyl-1,3,2-dioxaphospholane 2-oxide (2), for which a combination of the chiral ligands with either [Pd(Cp)(allyl)] or [Pd(allyl)(MeCN)2]+/NaCH(CO2Me)2 proves to be a convenient and active pre-catalyst system. A combination of an electron-rich phosphine moiety and an electron-deficient 3′-sulfone moiety provides the best enantioselectivity to date for this process, affording the branched 2-phenethenephosphonate, (-)-iso-3, in upto 74% ee with ligand (R,S)-10i, where Ar=p-anisyl and the 3′-SO2R groupis triflone.
Axially Chiral Biaryl Monophosphine Oxides Enabled by Palladium/WJ-Phos-Catalyzed Asymmetric Suzuki-Miyaura Cross-coupling
Ji, Wangqin,Wu, Hai-Hong,Zhang, Junliang
, p. 1548 - 1554 (2020/02/04)
A highly enantioselective palladium/WJ-Phos-catalyzed Suzuki-Miyaura coupling reaction for efficient construction of axially chiral biaryl monophosphine oxides was developed. A series of axially chiral biaryl monophosphine oxides were obtained in good yields and with high enantioselectivities. The practicability of this reaction was validated in the straightforward synthesis of axially chiral biaryl monophosphine ligand and demonstrated by a 100-g-scale synthesis. Moreover, various functionalizations of the product make it as a platform molecule for synthesis of other chiral biaryl phosphines.
Asymmetric ketone hydroboration catalyzed by alkali metal complexes derived from BINOL ligands
Carden, Jamie L.,Melen, Rebecca L.,Newman, Paul D.,Ruddy, Adam J.,Willcox, Darren
, p. 2417 - 2420 (2020/03/05)
The ability of alkali metal complexes featuring functionalized BINOL-derived ligands to catalyze ketone hydroboration reactions was explored. The reduced products were formed in excellent yields and with variable enantioselectivities dependent upon the nature of the ligand and the alkali metal cation.
Asymmetric hydrogenation of tert-alkyl ketones: DMSO effect in unification of stereoisomeric ruthenium complexes
Yamamura, Tomoya,Nakatsuka, Hiroshi,Tanaka, Shinji,Kitamura, Masato
supporting information, p. 9313 - 9315 (2013/09/12)
Face off: The ruthenium complexes of a new axially chiral PNNligand (L) are highly efficient in the presence of dimethylsulfoxide (DMSO) for hydrogenation of both functionalized and unfunctionalized tert-alkyl ketones. DMSO is thought to narrow down the many possible complex stereoisomers into a single facial L/Ru complex, thus enhancing the reactivity, selectivity, and productivity. Copyright
