17 research outputs found
Asymmetric Synthesis of <i>P</i>‑Stereogenic Diarylphosphinites by Palladium-Catalyzed Enantioselective Addition of Diarylphosphines to Benzoquinones
The reaction of phenyl(2,4,6-trimethylphenyl)phosphine
with a substituted benzoquinone in the presence of a chiral phosphapalladacycle
complex as a catalyst and triethylamine in chloroform at −45
°C proceeded in a new type of addition manner to give a high
yield of a 4-hydroxyphenyl phenyl(2,4,6-trimethylphenyl)phosphinite
with 98% enantioselectivity, which is a versatile intermediate readily
convertible into various phosphines and their derivatives with high
enantiomeric purity
Asymmetric Synthesis of <i>P</i>‑Stereogenic Diarylphosphinites by Palladium-Catalyzed Enantioselective Addition of Diarylphosphines to Benzoquinones
The reaction of phenyl(2,4,6-trimethylphenyl)phosphine
with a substituted benzoquinone in the presence of a chiral phosphapalladacycle
complex as a catalyst and triethylamine in chloroform at −45
°C proceeded in a new type of addition manner to give a high
yield of a 4-hydroxyphenyl phenyl(2,4,6-trimethylphenyl)phosphinite
with 98% enantioselectivity, which is a versatile intermediate readily
convertible into various phosphines and their derivatives with high
enantiomeric purity
Palladacycle-Catalyzed Asymmetric Hydrophosphination of Enones for Synthesis of C*- and P*-Chiral Tertiary Phosphines
A highly reactive and stereoselective hydrophosphination
of enones
catalyzed by palladacycles for the synthesis of C*- and P*-chiral
tertiary phosphines has been developed. When Ph<sub>2</sub>PH was
employed as the hydrophosphinating reagent, a series of C*-chiral
tertiary phosphines were synthesized (C*–P bond formation)
in high yields with excellent enantioselectivities, and a single recrystallization
provides access to their enantiomerically pure forms. When racemic
secondary phosphines <i>rac</i>-R<sup>3</sup>(R<sup>4</sup>)PH were utilized, a series of tertiary phosphines containing both
C*- and P*-chiral centers were generated (C*–P* bond formation)
in high yields with good diastereo- and enantioselectivities. The
stereoelectronic factors involved in the catalytic cycle have been
revealed
Metal Effects on the Asymmetric Cycloaddition Reaction between 3,4-Dimethyl-1-phenylphosphole and Sulfoxide
The
orthometalated [1-(dimethylamino)ethyl]naphthalene platinum(II) complex
has been used successfully to promote the asymmetric cycloaddition
reaction between 3,4-dimethyl-1-phenylphosphole and sulfoxide in high
selectivity. The <i>exo</i>-cycloadduct coordinated to the
platinum template as bidentate chelates via their phosphorus and sulfur
atoms. The dichloro platinum complexes could be crystallized and were
stable in the solid state as well as in solution. Optically pure P–S
bidentate ligands could be liberated from these dichloro complexes
by treatment with aqueous potassium cyanide. The study also highlights
the difference in reactivity and mode of substrate activation between
an earlier study involving a Pd analogue of the template and the current
results
Asymmetric Synthesis of Enaminophosphines via Palladacycle-Catalyzed Addition of Ph<sub>2</sub>PH to α,β-Unsaturated Imines
A highly reactive, chemo- and enantioselective addition
of diphenylphosphine to α,β-unsaturated imines catalyzed
by a palladacycle has been developed, thus providing the access to
a series of chiral tertiary enaminophosphines in high yields. A putative
catalytic cycle has also been proposed
Asymmetric Synthesis of Enaminophosphines via Palladacycle-Catalyzed Addition of Ph<sub>2</sub>PH to α,β-Unsaturated Imines
A highly reactive, chemo- and enantioselective addition
of diphenylphosphine to α,β-unsaturated imines catalyzed
by a palladacycle has been developed, thus providing the access to
a series of chiral tertiary enaminophosphines in high yields. A putative
catalytic cycle has also been proposed
Versatile Syntheses of Optically Pure PCE Pincer Ligands: Facile Modifications of the Pendant Arms and Ligand Backbones
A series of chiral C-stereogenic
PCP and PCN ligand precursors
were prepared in situ from inexpensive achiral starting materials
via a simple catalytic asymmetric P–H addition reaction in
good overall yields. This facile catalytic method of preparing the
ligand backbones renders easy and economical modifications of the
electronically crucial <i>para</i>-substituent, chiral functionalities,
and donor atoms for different transition metal ions. A one-pot synthetic
procedure was used efficiently to prepare the corresponding optically
pure pincer complexes. All the new complexes were characterized by
NMR and mass spectroscopy. The molecular structures of several selected
complexes have also been elucidated by X-ray crystallography. Preliminary
studies indicated that minor structural changes on these novel pincer
complexes affect their chemical properties significantly when they
were applied as catalysts for the reaction between diphenylphosphine
and chalcone
Asymmetric 1,4-Conjugate Addition of Diarylphosphines to α,β,γ,δ-Unsaturated Ketones Catalyzed by Transition-Metal Pincer Complexes
An
enantioselective asymmetric 1,4-addition of diarylphosphines
to linear α,β,γ,δ-unsaturated dienones was
developed. A series of chiral PCP- and PCN-transition-metal (Pd, Pt
and Ni) pincers, themselves prepared catalytically via asymmetric
hydrophosphination, were sequentially screened to reveal the roles
of backbone architecture and metal ion in catalyst design. The selected
ester-functionalized PCP-palladium pincer afforded the chiral 1,4-phosphine
adducts in excellent yields with up to >99% <i>ee</i>. The
same catalyst when utilized for the hydrophosphination of an α,β,γ,δ-unsaturated
malonate ester also revealed the critical role played by the ester
functionality on the ligand backbone in dictating the enantioselectivity
of the 1,6-adduct
Stereogenic Lock in 1‑Naphthylethanamine Complexes for Catalyst and Auxiliary Design: Structural and Reactivity Analysis for Cycloiridated Pseudotetrahedral Complexes
A series of optically
active pseudo-tetrahedral five-membered cyclometalated
1-naphthylethanamine iridium(III) complexes were prepared and characterized
to analyze the efficacy of the stereogenic conformational lock in
both solid and solution phases. The synthesis of the iridacycles was
diastereoselective, and the compounds were found to be conformationally
rigid. In comparison to its phenyl derivative, the structural lock
prevented oxidation of the amine moiety within the five-membered organometallic
ring during its synthesis. With up to three stereogenic centers in
one of the naphthalene complexes, the stereochemistry of the metallacycle
remained stable to both thermal and chemical changes. In terms of
catalytic performance, the complexes displayed excellent activity
for the asymmetric hydrogen transfer reaction, albeit with modest
enantioselectivities
Synthesis of Stereoprojecting, Chiral N‑C(sp<sup>3</sup>)‑E Type Pincer Complexes
A synthetic strategy
to generate chiral N-C(sp<sup>3</sup>)-E (E
= S, O) pincer complexes incorporating enhanced stereoprojecting groups
at the N-arm site has been established. The synthesis of the tridentate
pincer ligand was carried out via palladacycle-catalyzed asymmetric
hydrophosphination of N-chelating enones. The chelation properties
of the substrates were initially demonstrated on C(sp<sup>2</sup>)-N
type palladacycles. The extended substrate scope allows versatile
structural modifications on the ligand backbone. Subsequent cyclometalation
provided N-C(sp<sup>3</sup>)-E complexes in a diastereoselective reaction