1,039 research outputs found
Triorganoindium reagents in cross-coupling reactions: transition-metal-free reactions with benzopyranyl acetals and tetrahydroisoquinolines and solid-stable organometallics
Programa Oficial de Doutoramento en Química Ambiental e Fundamental. 5031V01[Abstract]
This Thesis presents the development of a new transition-metal-free coupling reaction of triorganoindium reagents with chromene and isochroman acetals under BF3·OEt2 activation. This reaction allows the synthesis of the corresponding 2-substituted 2H-chromenes and 1-substituted isochromans in good yields, in which aryl, heteroaryl, alkynyl, alkenyl, and alkyl groups can be transferred using only 50 mol% of the triorganoindium reagents. As an extension of this methodology, a transition-metal-free coupling reaction of triorganoindium reagents with N-protected tetrahydroisoquinolines (THIQs) under oxidative conditions is presented as well, where different aryl, heteroaryl, alkynyl, benzyl, and alkyl groups can be installed at the C-1 position of the THIQs, using only 50 mol% of the triorganoindium reagent. To demonstrate the synthetic utility of this reaction, it was applied to the synthesis of alkaloid Nuciferine.
This Thesis also presents the synthesis and isolation of solid, bench-stable triorganoindium reagents by coordination with 4-dimethylaminopyridine (DMAP). Different R3In·DMAP complexes bearing aryl, heteroaryl, alkynyl, and benzyl groups were prepared and then used in palladium-catalyzed cross-coupling reactions, where they reacted efficiently with diverse electrophiles including aryl, alkenyl, allyl, and benzyl bromides.[Resumen]
En esta Tesis se presenta el desarrollo de una nueva reacción de acoplamiento de reactivos triorganoíndicos con acetales de cromeno e isocramano mediante activación con BF3·OEt2 en ausencia de metales de transición. Esta reacción permite la síntesis de los correspondientes 2H-cromenos-2-sustituidos e isocromanos 1-sustituidos en buenos rendimientos, en donde grupos arilo, heteroarilo, alquinilo, alquenilo y alquilo se transfieren empleando solamente un 50 mol% de los reactivos triorganoíndicos. Como extensión de esta metodología, se presenta también la reacción de acoplamiento de reactivos triorganoíndicos con tetrahidroisoquinolinas (THIQs) N-protegidas en condiciones oxidantes y ausencia de metales de transición, en donde grupos arilo, heteroarilo, alquinilo, bencilo, y alquilo se acoplan en la posición C-1 de las THIQs, empleando solamente un 50 mol% del reactivo triorganoíndico. Para demostrar su utilidad sintética, esta nueva reacción se emplea en la síntesis del alcaloide Nuciferina.
En esta Tesis también se presenta la síntesis y aislamiento de reactivos triorganoíndicos sólidos y estables mediante coordinación con 4-dimetilaminopiridina (DMAP). Distintos R3In·DMAP con grupos arilo, heteroarilo, alquinilo y bencilo se preparan y son empleados en reacciones de acoplamiento cruzado catalizadas por paladio, donde reaccionan de forma eficiente con distintos electrófilos incluyendo bromuros de arilo, alquenilo, alilo y bencilo.[Resumo]
Nesta Tese presentamos o desenvolvemento dunha nova reacción de acoplamento de reactivos triorganoínicos con acetais de cromeno e isocromano pola activación con BF3·OEt2 en ausencia de metais de transición. Esta reacción permite a síntese dos correspondentes 2H-cromenos-2-sustituidos e isocromanos 1-sustituidos en bos rendementos, onde grupos arilo, heteroarilo, alquinilo, alquenilo y alquilo transfírense utilizando só un 50 mol% dos reactivos triorganoíndicos. Como extensión desta metodoloxía, presentamos tamén la reacción de reactivos triorganoíndicos con tetrahidroisoquinolinas N-protegidas, en condicións de oxidación e ausencia de metais de transición en que grupos arilo, heteroarilo, alquinilo, bencilo y alquilo pódense acoplar na posición C-1 das THIQs, utilizando só un 50 mol% dos reactivos triorganoíndicos. Para demostrar a súa utilidade sintética, a reacción emprégase na síntese do alcaloide Nuciferina.
Nesta Tese son sintetizados e illados reactivos triorganíndicos sólidos por coordinación con 4-dimetilaminopiridina (DMAP). Varios triorganoíndicos sólidos con grupos arilo, heteroarilo, alquinilo y bencilo prepáranse y son utilizados en reaccións de acoplamento cruzado catalizadas por paladio, reaccionando eficientemente con diferentes electrófilos incluíndo bromuros de arilo, alquenilo, alilo e bencilo
Reactividad de organometálicos de Indio(iii) con sistemas benzoheterocíclicos
[Resumen]En
este
trabajo
de
fin
de
máster
se
estudió
la
reactividad
de
varios
compuestos
benzoheterocíclicos
con
reactivos
triorganoíndicos
bajo
catálisis
con
complejos
de
níquel
y
bajo
activación
con
ácidos
de
Lewis.
Se
consiguió
llevar
a
cabo
la
reacción
de
acoplamiento
cruzado
de
trifenilindio
sobre
los
acetales
de
cromeno
y
quinolina
mediante
catálisis
con
níquel.
Probablemente
estas
reacciones
transcurran
a
través
de
intermedios
tipo
π-‐alil-‐níquel.
El
empleo
de
cantidades
subestequiométricas
del
reactivo
triorganíndico
demuestra
que
se
transfiere
de
manera
efectiva
más
de
un
grupo
orgánico
del
organometal
al
electrófilo.En
el
estudio
de
las
reacciones
con
ácidos
de
Lewis
se
encontró
que
utilizando
BF3·∙OEt2
es
posible
generar
nuevos
enlaces
carbono-‐carbono
en
los
acetales
benzoheterocíclicos
mediante
el
ataque
nucleófilo
de
reactivos
triorganíndicos
sobre
intermedios
oxocarbenio
o
azacarbenio.
Los
resultados
constituyen
el
primer
ejemplo
de
síntesis
de
cromenos-‐2-‐sustituidos
mediante
adición
nucleófila
de
organometales
(de
indio)
en
presencia
de
ácidos
de
Lewis,
en
donde
se
transfieren
grupos
arilo,
alquinilo
y
alquilo.[Abstract] In
this
master´s
final
project
the
reactivity
of
triorganoindium
species
towards
several
benzoheterocyclic
compounds
under
nickel
catalysis
and
under
Lewis
Acids
activation
was
studied.
The
cross-‐coupling
reaction
of
triphenylindium
with
chromene
and
quinoline
acetals
by
means
of
nickel
catalysis
was
achieved.
These
reactions
probably
take
place
through
π-‐allyl-‐
Ni
intermediates.
The
use
of
substoichiometric
quantities
of
the
triorganoindium
reagent
shows
that
more
than
one
organic
group
is
effectively
transferred
to
the
electrophile. Within
the
study
of
reactions
promoted
by
Lewis
Acids,
it
was
found
that
BF3·∙OEt2
allows
the
creation
of
new
carbon-‐carbon
bonds
in
the
benzoheterocyclic
compounds
via
nucleophilic
attack
of
oxocarbenium
or
azacarbenium
intermediates
by
triorganoindium
reagents.
These
results
are
the
first
examples
of
synthesis
of
2-‐substituted-‐chromenes
by
means
of
nucleophilic
addition
by
(indium)
organometallics
in
the
presence
of
a
Lewis
acid,
in
which
aryl,
alkynyl,
and
alkyl
groups
can
be
transferred.[Resumo] Neste
traballo
de
fin
de
máster
estudouse
a
reactividade
de
varios
compostos
benzoheterocíclicos
con
reactivos
triorganoíndicos
baixo
catálise
con
complexos
de
níquel
e
baixo
activación
con
ácidos
de
Lewis.
Conseguiuse
levar
a
cabo
a
reacción
de
axuste
cruzado
de
trifenilindio
sobre
os
acetais
de
cromeno
e
quinolina
mediante
catálise
con
níquel.
Probablemente
estas
reaccións
transcorran
a
través
de
intermedios
tipo
π-‐alil-‐níquel.
O
emprego
de
cantidades
subestequiométricas
do
reactivo
triorganoíndico
demostra
que
se
transfire
de
maneira
efectiva
máis
dun
grupo
orgánico
do
organometai
ao
electrófilo. No
estudo
das
reaccións
con
ácidos
de
Lewis
descubriuse
que
utilizando
BF3·∙OEt2
é
posible
xerar
novos
enlaces
carbono-‐carbono
nos
acetales
benzoheterocíclicos
mediante
o
ataque
nucleófilo
de
reactivos
triorganíndicos
sobre
intermedios
oxocarbenio
ou
azacarbenio.
Os
resultados
constitúen
o
primeiro
exemplo
de
síntese
de
cromenos-‐2-‐substituídos
mediante
adición
nucleófila
de
organometais
(de
indio)
en
presenza
de
ácidos
de
Lewis,
onde
se
transfiren
grupos
arilo,
alquinilo
e
alquilo.Traballo fin de mestrado (UDC.CIE). Ciencias, tecnoloxías e xestión ambiental. Curso 2013/201
Synthesis of bench-stable solid triorganoindium reagents and reactivity in palladium-catalyzed cross-coupling reactions
[Abstract] Bench-stable solid triorganoindium compounds have been prepared by coordination with 4-(dimethylamino)pyridine (DMAP). The solid R3In(DMAP) complexes are obtained from the corresponding solution of R3In in quantitative yield and can be stored for up to several weeks. These reagents show excellent reactivity in palladium-catalyzed cross-coupling reactions with organic electrophiles.Ministerio de Economía y Competitividad; CTQ2015-68369-PGalicia. Consellería de Cultura, Educación e Ordenación Universitaria; GRC2014/04
Transition-metal-free cross-coupling of indium organometallics with chromene and isochroman acetals mediated by BF3·OEt2
[Abstract] A transition-metal-free coupling of triorganoindium reagents with benzopyranyl acetals mediated by a Lewis acid has been developed. The reaction of R3In with chromene and isochroman acetals in the presence of BF3·OEt2 afforded 2-substituted chromenes and 1-substituted isochromans, respectively, in good yields. The reactions proceed with a variety of triorganoindium reagents (aryl, heteroaryl, alkynyl, alkenyl, alkyl) using only 50 mol % of the organometallic, thus demonstrating the efficiency of these species. Preliminary mechanistic studies indicate the formation of an oxocarbenium ion intermediate in the presence of the Lewis acid.Ministerio de Economía y Competitividad; CTQ2012-31200Ministerio de Economía y Competitividad; CTQ2015-68369-
Sloan Digital Sky Survey IV: Mapping the Milky Way, Nearby Galaxies, and the Distant Universe
We describe the Sloan Digital Sky Survey IV (SDSS-IV), a project encompassing three major spectroscopic programs. The Apache Point Observatory Galactic Evolution Experiment 2 (APOGEE-2) is observing hundreds of thousands of Milky Way stars at high resolution and high signal-to-noise ratios in the near-infrared. The Mapping Nearby Galaxies at Apache Point Observatory (MaNGA) survey is obtaining spatially resolved spectroscopy for thousands of nearby galaxies (median ). The extended Baryon Oscillation Spectroscopic Survey (eBOSS) is mapping the galaxy, quasar, and neutral gas distributions between and 3.5 to constrain cosmology using baryon acoustic oscillations, redshift space distortions, and the shape of the power spectrum. Within eBOSS, we are conducting two major subprograms: the SPectroscopic IDentification of eROSITA Sources (SPIDERS), investigating X-ray AGNs and galaxies in X-ray clusters, and the Time Domain Spectroscopic Survey (TDSS), obtaining spectra of variable sources. All programs use the 2.5 m Sloan Foundation Telescope at the Apache Point Observatory; observations there began in Summer 2014. APOGEE-2 also operates a second near-infrared spectrograph at the 2.5 m du Pont Telescope at Las Campanas Observatory, with observations beginning in early 2017. Observations at both facilities are scheduled to continue through 2020. In keeping with previous SDSS policy, SDSS-IV provides regularly scheduled public data releases; the first one, Data Release 13, was made available in 2016 July
Sloan Digital Sky Survey IV: mapping the Milky Way, nearby galaxies, and the distant universe
We describe the Sloan Digital Sky Survey IV (SDSS-IV), a project encompassing three major spectroscopic programs. The Apache Point Observatory Galactic Evolution Experiment 2 (APOGEE-2) is observing hundreds of thousands of Milky Way stars at high resolution and high signal-to-noise ratios in the near-infrared. The Mapping Nearby Galaxies at Apache Point Observatory (MaNGA) survey is obtaining spatially resolved spectroscopy for thousands of nearby galaxies (median ). The extended Baryon Oscillation Spectroscopic Survey (eBOSS) is mapping the galaxy, quasar, and neutral gas distributions between and 3.5 to constrain cosmology using baryon acoustic oscillations, redshift space distortions, and the shape of the power spectrum. Within eBOSS, we are conducting two major subprograms: the SPectroscopic IDentification of eROSITA Sources (SPIDERS), investigating X-ray AGNs and galaxies in X-ray clusters, and the Time Domain Spectroscopic Survey (TDSS), obtaining spectra of variable sources. All programs use the 2.5 m Sloan Foundation Telescope at the Apache Point Observatory; observations there began in Summer 2014. APOGEE-2 also operates a second near-infrared spectrograph at the 2.5 m du Pont Telescope at Las Campanas Observatory, with observations beginning in early 2017. Observations at both facilities are scheduled to continue through 2020. In keeping with previous SDSS policy, SDSS-IV provides regularly scheduled public data releases; the first one, Data Release 13, was made available in 2016 July
Sloan Digital Sky Survey IV : mapping the Milky Way, nearby galaxies, and the distant universe
We describe the Sloan Digital Sky Survey IV (SDSS-IV), a project encompassing three major spectroscopic programs. The Apache Point Observatory Galactic Evolution Experiment 2 (APOGEE-2) is observing hundreds of thousands of Milky Way stars at high resolution and high signal-to-noise ratios in the near-infrared. The Mapping Nearby Galaxies at Apache Point Observatory (MaNGA) survey is obtaining spatially resolved spectroscopy for thousands of nearby galaxies (median z ~ 0.03). The extended Baryon Oscillation Spectroscopic Survey (eBOSS) is mapping the galaxy, quasar, and neutral gas distributions between z ~ 0.6 and 3.5 to constrain cosmology using baryon acoustic oscillations, redshift space distortions, and the shape of the power spectrum. Within eBOSS, we are conducting two major subprograms: the SPectroscopic IDentification of eROSITA Sources (SPIDERS), investigating X-ray AGNs and galaxies in X-ray clusters, and the Time Domain Spectroscopic Survey (TDSS), obtaining spectra of variable sources. All programs use the 2.5 m Sloan Foundation Telescope at the Apache Point Observatory; observations there began in Summer 2014. APOGEE-2 also operates a second near-infrared spectrograph at the 2.5 m du Pont Telescope at Las Campanas Observatory, with observations beginning in early 2017. Observations at both facilities are scheduled to continue through 2020. In keeping with previous SDSS policy, SDSS-IV provides regularly scheduled public data releases; the first one, Data Release 13, was made available in 2016 July
Recommended from our members
Sloan Digital Sky Survey IV: Mapping the Milky Way, Nearby Galaxies, and the Distant Universe
We describe the Sloan Digital Sky Survey IV (SDSS-IV), a project encompassing
three major spectroscopic programs. The Apache Point Observatory Galactic
Evolution Experiment 2 (APOGEE-2) is observing hundreds of thousands of Milky
Way stars at high resolution and high signal-to-noise ratio in the
near-infrared. The Mapping Nearby Galaxies at Apache Point Observatory (MaNGA)
survey is obtaining spatially-resolved spectroscopy for thousands of nearby
galaxies (median redshift of z = 0.03). The extended Baryon Oscillation
Spectroscopic Survey (eBOSS) is mapping the galaxy, quasar, and neutral gas
distributions between redshifts z = 0.6 and 3.5 to constrain cosmology using
baryon acoustic oscillations, redshift space distortions, and the shape of the
power spectrum. Within eBOSS, we are conducting two major subprograms: the
SPectroscopic IDentification of eROSITA Sources (SPIDERS), investigating X-ray
AGN and galaxies in X-ray clusters, and the Time Domain Spectroscopic Survey
(TDSS), obtaining spectra of variable sources. All programs use the 2.5-meter
Sloan Foundation Telescope at Apache Point Observatory; observations there
began in Summer 2014. APOGEE-2 also operates a second near-infrared
spectrograph at the 2.5-meter du Pont Telescope at Las Campanas Observatory,
with observations beginning in early 2017. Observations at both facilities are
scheduled to continue through 2020. In keeping with previous SDSS policy,
SDSS-IV provides regularly scheduled public data releases; the first one, Data
Release 13, was made available in July 2016
Optimasi Portofolio Resiko Menggunakan Model Markowitz MVO Dikaitkan dengan Keterbatasan Manusia dalam Memprediksi Masa Depan dalam Perspektif Al-Qur`an
Risk portfolio on modern finance has become increasingly technical, requiring the use of sophisticated mathematical tools in both research and practice. Since companies cannot insure themselves completely against risk, as human incompetence in predicting the future precisely that written in Al-Quran surah Luqman verse 34, they have to manage it to yield an optimal portfolio. The objective here is to minimize the variance among all portfolios, or alternatively, to maximize expected return among all portfolios that has at least a certain expected return. Furthermore, this study focuses on optimizing risk portfolio so called Markowitz MVO (Mean-Variance Optimization). Some theoretical frameworks for analysis are arithmetic mean, geometric mean, variance, covariance, linear programming, and quadratic programming. Moreover, finding a minimum variance portfolio produces a convex quadratic programming, that is minimizing the objective function ðð¥with constraintsð ð 𥠥 ðandð´ð¥ = ð. The outcome of this research is the solution of optimal risk portofolio in some investments that could be finished smoothly using MATLAB R2007b software together with its graphic analysis
Impacts of the Tropical Pacific/Indian Oceans on the Seasonal Cycle of the West African Monsoon
The current consensus is that drought has developed in the Sahel during the second half of the twentieth century as a result of remote effects of oceanic anomalies amplified by local land–atmosphere interactions. This paper focuses on the impacts of oceanic anomalies upon West African climate and specifically aims to identify those from SST anomalies in the Pacific/Indian Oceans during spring and summer seasons, when they were significant. Idealized sensitivity experiments are performed with four atmospheric general circulation models (AGCMs). The prescribed SST patterns used in the AGCMs are based on the leading mode of covariability between SST anomalies over the Pacific/Indian Oceans and summer rainfall over West Africa. The results show that such oceanic anomalies in the Pacific/Indian Ocean lead to a northward shift of an anomalous dry belt from the Gulf of Guinea to the Sahel as the season advances. In the Sahel, the magnitude of rainfall anomalies is comparable to that obtained by other authors using SST anomalies confined to the proximity of the Atlantic Ocean. The mechanism connecting the Pacific/Indian SST anomalies with West African rainfall has a strong seasonal cycle. In spring (May and June), anomalous subsidence develops over both the Maritime Continent and the equatorial Atlantic in response to the enhanced equatorial heating. Precipitation increases over continental West Africa in association with stronger zonal convergence of moisture. In addition, precipitation decreases over the Gulf of Guinea. During the monsoon peak (July and August), the SST anomalies move westward over the equatorial Pacific and the two regions where subsidence occurred earlier in the seasons merge over West Africa. The monsoon weakens and rainfall decreases over the Sahel, especially in August.Peer reviewe
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