Catalytic synthesis of vinylphosphanes via calcium-mediated intermolecular hydrophosphanylation of alkynes and butadiynes

Al‐Shboul, Tareq M. A.; Pálfi, Villö K.; Yu, Lian; Kretschmer, Robert; Wimmer, Katja; Fischer, R.; Görls, Helmar; Reiher, Markus; Westerhausen, Matthias

doi:10.1016/j.jorganchem.2010.08.058

Cited by 40 publications

(13 citation statements)

References 70 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The only catalysts based on heavy alkaline earth metals for the hydrophosphination of alkynes are derived from calcium [ 123 , 252 – 253 ]. A similar behavior of calcium(II) and ytterbium(II) compounds seems possible as the oxidation state of Yb(II) does not change during the ytterbium(II)-catalyzed hydrophosphination of alkynes.…”

Section: Reviewmentioning

confidence: 99%

Preparation of phosphines through C–P bond formation

Wauters¹,

Debrouwer²,

Stevens³

2014

Beilstein J. Org. Chem.

164

View full text Add to dashboard Cite

show abstract

Section: Reviewmentioning

confidence: 99%

Preparation of phosphines through C–P bond formation

Wauters¹,

Debrouwer²,

Stevens³

2014

Beilstein J. Org. Chem.

164

View full text Add to dashboard Cite

show abstract

“…180 [(THF) 4 Ca(PPh 2 ) 2 ] has been shown to be a very effective catalyst for the hydrophosphination of substituted alkynes. 181,182 Alkylstrontium amidoboranes have been shown to undergo b-hydride elimination and Sr-C insertion reactions; observations which provide support for similar processes in d 0 -catalysed dialkylamine borane dehydrocoupling. 183 [Ca(BH 4 )(THF) 5 ][BPh 4 ] and a series of well-defined compounds containing Ae.…”

Section: Group 16 Donorsmentioning

confidence: 91%

Alkaline and alkaline earth metals

Hill

2012

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

View full text Add to dashboard Cite

Advances made during the calendar year 2011 relating to the coordination and inorganic chemistry of the elements of Groups 1 and 2 are summarised in this non-critical review. Coverage concentrates on topics centred around the synthesis, and applications of coordination and organometallic compounds of these elements. HighlightsThe isolation and reaction chemistry of kinetically-stabilised Group 2 species in which the alkaline earth centre exists in a formal +1 oxidation state has received intense international attention while interest in the potential of alkaline earth complexes as benign and inexpensive reagents for catalysis has continued to develop. LithiumA review of the resting-state structures of organocuprates determined using X-ray crystallography has appeared. 1 The electronic stability of s-block benzylates and di-and tri-phenylmethanide derivatives has been reviewed. 2 Reactions of the lithium boryl LiB(DippNCHQCHNDipp) with organohalides (RX) giving RB(DippNCHQCHNDipp) have been studied using DFT calculations. 3 Group 14 donor ligands An X-ray diffraction analysis of tetrareduced corannulene, C 20 H 10 4À , has confirmed the formation of a sandwich-type supramolecular aggregate in which five Li + ions are sandwiched between the two tetrareduced corannulene decks. 4 A combined experimental and DFT study has predicted that benzyl anions with strong p-withdrawing groups in the meta position have low energy diradical or triplet electronic states. 5 A lithium complex of an abnormal carbene with the composition [H 3 BC{{N(2, Pr 2 )C 6 H 3 } 2 )CHCLi(THF) 3 }] has been synthesised by lithiation of the NHC borane adduct. 6 Diastereomeric oxazolinylaziridines (R,R)-9 and (R,S)-9 have been regioselectively lithiated at the a-position with respect to the oxazolinyl ring. 7 Computational studies of the carbolithiation of b-methylstyrene with

show abstract

“…Moreover, of note is the fact that, as illustrated in Scheme 53, single hydrophosphination of unsymmetrical diynes was successfully achieved, with high regio-and stereocontrol, by performing the reactions at −78 • C with an equimolar amount of diphenylphosphine. Double hydrophosphination reactions of 1,3-diynes RC≡CC≡CR (R = Me, t Bu, SiMe 3 , Ph, 2,4,6-C 6 H 2 Me 3 ) with diphenylphosphine catalyzed by the phosphido-calcium complex [Ca(THF) 4 (PPh 2 ) 2 ] were additionally described by Westerhausen and colleagues [142,143]. A low selectivity was, in general, observed, the reactions leading to complex mixtures containing the corresponding 1,4-bis(diphenylphosphino)-1,3-dienes 99 (major products), along with the 1,2-bis(diphenylphosphino)-1,3-dienes 100 (the four possible stereoisomers) and, in some cases, the allenic derivative 101 (see Figure 13).…”

Section: Hydrophosphination and Hydrophosphorylation Processesmentioning

confidence: 99%

Catalytic Hydrofunctionalization Reactions of 1,3-Diynes

Cadierno

2022

Catalysts

View full text Add to dashboard Cite

Metal-catalyzed hydrofunctionalization reactions of alkynes, i.e., the addition of Y–H units (Y = heteroatom or carbon) across the carbon–carbon triple bond, have attracted enormous attention for decades since they allow the straightforward and atom-economic access to a wide variety of functionalized olefins and, in its intramolecular version, to relevant heterocyclic and carbocyclic compounds. Despite conjugated 1,3-diynes being considered key building blocks in synthetic organic chemistry, this particular class of alkynes has been much less employed in hydrofunctionalization reactions when compared to terminal or internal monoynes. The presence of two C≡C bonds in conjugated 1,3-diynes adds to the classical regio- and stereocontrol issues associated with the alkyne hydrofunctionalization processes’ other problems, such as the possibility to undergo 1,2-, 3,4-, or 1,4-monoadditions as well as double addition reactions, thus increasing the number of potential products that can be formed. In this review article, metal-catalyzed hydrofunctionalization reactions of these challenging substrates are comprehensively discussed.

show abstract

Catalytic synthesis of vinylphosphanes via calcium-mediated intermolecular hydrophosphanylation of alkynes and butadiynes

Cited by 40 publications

References 70 publications

Preparation of phosphines through C–P bond formation

Preparation of phosphines through C–P bond formation

Alkaline and alkaline earth metals

Catalytic Hydrofunctionalization Reactions of 1,3-Diynes

Contact Info

Product

Resources

About