Ligand survey results in identification of PNP pincer complexes of iridium as long-lived and chemoselective catalysts for dehydrogenative borylation of terminal alkynes

Lee, Chun‐I; DeMott, Jessica C.; Pell, Christopher J.; Christopher, Alyson; Zhou, Jia; Bhuvanesh, Nattamai; Ozerov, Oleg V.

doi:10.1039/c5sc02161h

Cited by 54 publications

(48 citation statements)

References 81 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…7 Platinum is rarely mentioned in the field of dehydrogenative borylation, but has been shown to catalyse the dehydrogenative borylation of olefins with borane clusters. 10 A slower DHBTA catalysis with a similar scope was reported by Tsuchimoto et al using Zn(OTf ) 2 /pyridine. Alkynylboronates are widely applicable in organic synthesis and their use has recently been reviewed.…”

supporting

confidence: 63%

Catalytic dehydrogenative borylation of terminal alkynes by POCOP-supported palladium complexes

Pell

Ozerov

2015

Inorg. Chem. Front.

Self Cite

View full text Add to dashboard Cite

A (POCOP)-supported palladium complex was used to catalyse the dehydrogenative borylation of terminal alkynes to form alkynylboronates. Competing hydrogenation reactions could be mitigated through the use of additives such as phosphines or elemental mercury. Scheme 1 Dehydrogenative borylation of terminal alkynes.Scheme 2 POCOP-supported Ni, Pd, and Pt precatalysts. † Electronic supplementary information (ESI) available: Experimental details and spectroscopic characterization. See

show abstract

supporting

confidence: 63%

Catalytic dehydrogenative borylation of terminal alkynes by POCOP-supported palladium complexes

Pell

Ozerov

2015

Inorg. Chem. Front.

Self Cite

View full text Add to dashboard Cite

show abstract

“…This reaction showed high chemical selectivity, and no other side reactions, such as hydrogenation and hydroboration, occurred . Later, the authors investigated the ligand effect and found that an unsymmetrical PNP‐supported iridium complex could also efficiently catalyzed this reaction with only a 0.025 mol % loading of catalyst . Good to excellent yields were obtained for aryl, alkyl and silyl acetylenes, even including propargyl derivatives and 1,6‐enynes.…”

Section: Formation Of Spc−heteroatom Bondsmentioning

confidence: 99%

Cross‐Dehydrogenative Alkynylation: A Powerful Tool for the Synthesis of Internal Alkynes

et al. 2020

View full text Add to dashboard Cite

show abstract

“…Alkynyl boronates can be prepared from monovalent alcohols [10,11], but due to their increased hydrolytic stability the incorporation of bifunctional chelating alcohols, in particular 1,2-dihydroxy compounds, is highly preferred. Thus, the bivalent alcohols introduce a bridging backbone leading to improved stability, and the scope of 1,2-diols employed for alkynyl boronate esters includes pinacol ( 1 ) [12,13,14,15,16,17,18,19], catechol, ( 2 ) [20,21,22], and ethylene glycol ( 3 ) [23,24], Scheme 1. These compounds 1 – 3 may also be considered as boron substituted heterocycles and can be viewed as derivatives of the parent 1,3,2-dioxaborolane.…”

Section: Introductionmentioning

confidence: 99%

N-Heterocyclic Carbene Adducts of Alkynyl Functionalized 1,3,2-Dithioborolanes

2019

View full text Add to dashboard Cite

Alkynyl functionalized boron compounds are versatile intermediates in the areas of medicinal chemistry, materials science, and optical materials. In particular, alkynyl boronate esters [R1−C≡C−B(OR2)2] are of interest since they provide reactivity at both the alkyne entity, with retention of the B−C bond or alkyne transfer to electrophilic substrates with scission of the latter. The boron atom is commonly well stabilized due to (i) the extraordinary strength of two B−O bonds, and (ii) the chelate effect exerted by a bifunctional alcohol. We reasoned that the replacement of a B−O for a B−S bond would lead to higher reactivity and post-functionalization in the resulting alkynyl boronate thioesters [R1−C≡C−B(S2X)]. Access to this poorly investigated class of compounds starts form chloro dithioborolane cyclo-Cl−B(S2C2H4) as a representative example. Whereas syntheses of three coordinate alkynyl boronate thioesters [R1−C≡C−B(S2X)] proved to be ineffective, the reactions of NHC-adducts (NHC = N-heterocyclic carbene) of cyclo-Cl-B(S2C2H4) afforded the alkyne substituted thioboronate esters in good yield. The products NHC−B(S2C2H4)(C≡C-R1) are remarkably stable towards water and air, which suggests their use as boron-based building blocks for applications akin to oxygen-based boronate esters.

show abstract

Ligand survey results in identification of PNP pincer complexes of iridium as long-lived and chemoselective catalysts for dehydrogenative borylation of terminal alkynes

Abstract: A new, highly active Ir catalyst for dehydrogenative borylation of terminal alkynes (DHBTA) has been identified.

Cited by 54 publications

References 81 publications

Catalytic dehydrogenative borylation of terminal alkynes by POCOP-supported palladium complexes

Catalytic dehydrogenative borylation of terminal alkynes by POCOP-supported palladium complexes

Cross‐Dehydrogenative Alkynylation: A Powerful Tool for the Synthesis of Internal Alkynes

N-Heterocyclic Carbene Adducts of Alkynyl Functionalized 1,3,2-Dithioborolanes

Contact Info

Product

Resources

About