Hexafluoroisopropanol for the Selective Deactivation of Poisonous Nucleophiles Enabling Catalytic Asymmetric Cyclopropanation of Complex Molecules

Sharland, Jack C.; Dunstan, David I.; Majumdar, Dyuti; Gao, Jin; Tan, Kian L.; Malik, Hasnain A.; Davies, Huw M. L.

doi:10.1021/acscatal.2c03909

Cited by 11 publications

(4 citation statements)

References 95 publications

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“…A feature of our ligand design is the ability to monitor the coordination of a variety of species at one Rh site, and allows the evaluation of effect of the tethered, axial coordinating group at the other Rh site. This could have implications where initial coordination is important, such as competition between carbene precursors and catalyst poisons in carbene transfer reactions, [14] or off‐targeted binding of proteins in a biological context [8a,10b] . Our recent work has shown that incorporating tethered, axially coordinated thioether ligands can improve yields in cyclopropanation reactions [15] and Si−H insertion reactions [16] .…”

Section: Introductionmentioning

confidence: 99%

Effect of Tethered Sulfur Ligands on the Association Constants of Dirhodium(II,II) Paddlewheel Complexes

Moore,

Ogunyemi,

Nalaoh

et al. 2023

Eur J Inorg Chem

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Herein we report on the association constants (Ka) of dirhodium(II,II) complexes bearing tethered thioether or sulfoxide ligands in the presence of binding analytes. The effect of substituent and tether length modifications on Ka and the stability of the complexes were analyzed by UV‐vis using pyridine and cysteine as binding analytes of interest. When pyridine was the incoming exogenous species, dirhodium(II,II) complexes with tethered sulfur ligands reduced the axial coordination of pyridine by up to four‐fold when compared to dirhodium(II,II) complexes without tethered axial coordination. Tuning the tethered sulfur coordination through changes in tether length, substituent, and electronics resulted in Ka values that spanned 2.6×103 M−1 to 8.1×103 M−1. The differences in Ka were correlated with structural features of crystals obtained from single crystal X‐ray diffraction and results pointed to release of strain as a factor in the association constants. Interestingly, cysteine interactions were greater for complexes with tethered, axial ligands than those without, alluding to an alternate mode of coordination with cysteine. These results demonstrate the tunability of tethered, axial coordination on dirhodium(II,II) paddlewheel complexes and provide access to controlled binding of exogenous species.

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Section: Introductionmentioning

confidence: 99%

Effect of Tethered Sulfur Ligands on the Association Constants of Dirhodium(II,II) Paddlewheel Complexes

Moore,

Ogunyemi,

Nalaoh

et al. 2023

Eur J Inorg Chem

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“…In developing this method, we also tested the sensitivity of the reaction to additional changes of conditions (sensitivity screen; Scheme b). Employing a radar plot, we evaluated the reaction performance with the introduction of air and water, and variable temperature and current were assessed (Scheme b). Yield of product 2 was compared to the optimized reaction conditions (Table , entry 9) .…”

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confidence: 99%

Sacrificial Anode-Free Electrochemical Cross-Electrophile Coupling of 1,3-Diol Derivatives to Form Aliphatic and Aryl Cyclopropanes

Hirbawi,

Raffman,

Pedroarena

et al. 2024

Org. Lett.

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Cross-electrophile coupling reactions that forge C(sp 3 )−C(sp 3 ) bonds are strategic methods for the synthesis of molecules with high F(sp 3 ), yet very few employ electrochemical conditions as the necessary reductant. Herein, we report an electrochemical intramolecular cross-electrophile coupling reaction of 1,3-diol derivatives to access aliphatic and aryl cyclopropanes, including spirocyclic and fused bicyclic cyclopropanes. The scalable electrochemical cross-electrophile coupling (eXEC) reaction employs a nonsacrificial anode in an undivided cell.

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“…The positive influence of HFIP is consistent with recent studies, demonstrating that in the reactions of donor/acceptor carbenes HFIP blocks interference by water 30 and a range of other nucleophilic poisons. 31 Having demonstrated that the C−H functionalization of benzylic sites with the diazophosphonate 4 is a viable process, an optimization study with a series of the most established chiral catalysts was conducted (Table 1 and Figure 1). The bulky triarylcyclopropanecarboxylate catalyst, Rh 2 (S-p-Br-TPCP) 4 , 32 gave only a trace of the desired product 6 (entry 2) even though it is an exceptional catalyst for C−H functionalization reactions with aryldiazoacetates.…”

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confidence: 99%

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confidence: 99%

Enantioselective Intermolecular C–H Functionalization of Primary Benzylic C–H Bonds Using ((Aryl)(diazo)methyl)phosphonates

Naeem,

Matsuo,

Davies

2023

ACS Catal.

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Catalyst-controlled C−H functionalization using donor/acceptor carbenes has been shown to be an efficient process capable of high levels of site control and stereocontrol. This study demonstrated that the scope of the donor/acceptor carbene C−H functionalization can be extended to systems where the acceptor group is a phosphonate. When using the optimized dirhodium catalyst, Rh 2 (S-di-(4-Br)TPPTTL) 4 , ((aryl)(diazo)methyl)phosphonates undergo highly enantioselective (84−99% ee) and site-selective (>30:1 r.r.) benzylic C−H functionalization. The phosphonate group is much more sterically demanding than the previously studied carboxylate ester group, leading to much higher selectivity for a primary site versus more sterically crowded positions. The effectiveness of this methodology has been demonstrated by the late-stage primary C−H functionalization of estrone, adapalene, (S)-naproxen, clofibrate, and gemfibrozil derivatives.

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Hexafluoroisopropanol for the Selective Deactivation of Poisonous Nucleophiles Enabling Catalytic Asymmetric Cyclopropanation of Complex Molecules

Cited by 11 publications

References 95 publications

Effect of Tethered Sulfur Ligands on the Association Constants of Dirhodium(II,II) Paddlewheel Complexes

Effect of Tethered Sulfur Ligands on the Association Constants of Dirhodium(II,II) Paddlewheel Complexes

Sacrificial Anode-Free Electrochemical Cross-Electrophile Coupling of 1,3-Diol Derivatives to Form Aliphatic and Aryl Cyclopropanes

Enantioselective Intermolecular C–H Functionalization of Primary Benzylic C–H Bonds Using ((Aryl)(diazo)methyl)phosphonates

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