Tetraethylphosphorodiamidate-Directed Metalation Group: Directed <i>Ortho</i> and Remote Metalation, Cross Coupling, and Remote Phospha Anionic Fries Rearrangement Reactions

Patel, Jignesh J.; Blackburn, Thomas; Alessi, Manlio; Sawinski, Hannah; Snieckus, Victor

doi:10.1021/acs.orglett.0c01123

Cited by 9 publications

(5 citation statements)

References 68 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The phosphorodiamidate groups of BINOL can direct the ortho-lithiation-iodonation at 3,3′positions (Scheme 107). 330 After the BINOL-phosphorodiamidate was treated with 2.5 equiv of s BuLi in THF at −78 °C for 90 min, it was quenched with the addition of I 2 to give the diiodide 310 in 39% yield.…”

Section: Reactions Of Binol Carbamatesmentioning

confidence: 99%

Regioselective Substitution of BINOL

2024

Chem. Rev.

View full text Add to dashboard Cite

1,1′-Bi-2-naphthol (BINOL) has been extensively used as the chirality source in the fields of molecular recognition, asymmetric synthesis, and materials science. The direct electrophilic substitution at the aromatic rings of the optically active BINOL has been developed as one of the most convenient strategies to structurally modify BINOL for diverse applications. High regioselectivity has been achieved for the reaction of BINOL with electrophiles. Depending upon the reaction conditions and substitution patterns, various functional groups can be introduced to the specific positions, such as the 6-, 5-, 4-, and 3-positions, of BINOL. Ortho-lithiation at the 3-position directed by the functional groups at the 2-position of BINOL have been extensively used to prepare the 3- and 3,3′-substituted BINOLs. The use of transition metal-catalyzed C–H activation has also been explored to functionalize BINOL at the 3-, 4-, 5-, 6-, and 7-positions. These regioselective substitutions of BINOL have allowed the construction of tremendous amount of BINOL derivatives with fascinating structures and properties as reviewed in this article. Examples for the applications of the optically active BINOLs with varying substitutions in asymmetric catalysis, molecular recognition, chiral sensing and materials are also provided.

show abstract

Section: Reactions Of Binol Carbamatesmentioning

confidence: 99%

Regioselective Substitution of BINOL

2024

Chem. Rev.

View full text Add to dashboard Cite

show abstract

“…Since its discovery, the anionic phospha-Fries rearrangement has been used as a cornerstone to synthesize lithium borates as promising materials for lithium-ion batteries [ 146 ] and receptors for the complexation of lanthanides [ 147 ] and other transition metals [ 148 , 149 ]. Recently, Snieckus’s group reported an anionic phospha Fries rearrangement of aryl tetraethylphosphorodiamidates [ 150 , 151 ]. A review of the phospha-Fries rearrangement was published in 2005 [ 152 ]; therefore, this chapter summarizes recent findings in this area.…”

Section: Organophosphate Rearrangementsmentioning

confidence: 99%

Organophosphates as Versatile Substrates in Organic Synthesis

Oeser,

Tobrman

2024

Molecules

View full text Add to dashboard Cite

This review summarizes the applications of organophosphates in organic synthesis. After a brief introduction, it discusses cross-coupling reactions, including both transition-metal-catalyzed and transition-metal-free substitution reactions. Subsequently, oxidation and reduction reactions are described. In addition, this review highlights the applications of organophosphates in the synthesis of natural compounds, demonstrating their versatility and importance in modern synthetic chemistry.

show abstract

“…On the other hand, directed ortho-lithiation is a powerful methodology in organic synthesis for the regioselective functionalization of (hetero)aromatics [12,13], and the search for new directed metalation groups is a topic actively explored [14][15][16]. In 2005, our group described a tandem Sonogashira coupling/5-endo-dig cyclization reaction of 2iodo-3-halophenols, which were prepared through the regioselective ortho-lithiation of N,Ndiethyl O-3-halophenylcarbamates [17].…”

Section: Introductionmentioning

confidence: 99%

“…EI-LRMS m/z (%): 264 (M + + 2, 64), 262 (M + , 100), 199(22), 163(24). APCI-HRMS was calculated for C14 H 9 Cl 2 O [M + H] + 263.0025, and found 263.0028. 4-Chloro-5-fluoro-2-phenylbenzo[b]furan (3fa): The reaction of O-3,4-difluorophenyl N,Ndiethylcarbamate (1f) (245 mg, 1 mmol), following the general procedure with Method A, yielded the product as a light yellow solid (57% yield); mp = 103-105 • C; R f = 0.13 (hexane/EtOAc, 10:1).…”

mentioning

confidence: 99%

Transition Metal-Free Synthesis of Halobenzo[b]furans from O-Aryl Carbamates via o-Lithiation Reactions

et al. 2022

View full text Add to dashboard Cite

A straightforward and transition metal-free one-pot protocol to synthesize halobenzo[b]furans has been developed employing simple and easily available starting materials such as O-aryl carbamates and alkynylsulfones. The fine-tuning of the different steps involved was key to achieving a successful one-pot procedure. Initially, a directed ortho-lithiation process, which uses the carbamate as the directed metalation group, was crucial in providing access to O-2-alkynylaryl N,N-diethyl carbamates by a direct alkynylation of the o-lithiated carbamate, with arylsulfonylalkynes as electrophilic reagents. Cyclization of the generated o-alkynylaryl carbamates was successfully accomplished through a strategy involving in situ carbamate alkaline hydrolysis under conventional heating or microwave irradiation, coupled with a subsequent heterocyclization step delivering the desired benzo[b]furans. A wide variety of new halobenzo[b]furans has been synthesized and their utility has been demonstrated by their further transformation.

show abstract

Tetraethylphosphorodiamidate-Directed Metalation Group: Directed Ortho and Remote Metalation, Cross Coupling, and Remote Phospha Anionic Fries Rearrangement Reactions

Cited by 9 publications

References 68 publications

Regioselective Substitution of BINOL

Regioselective Substitution of BINOL

Organophosphates as Versatile Substrates in Organic Synthesis

Transition Metal-Free Synthesis of Halobenzo[b]furans from O-Aryl Carbamates via o-Lithiation Reactions

Contact Info

Product

Resources

About