Borane Addition Compounds of Bases

Moore, R. L.; White, Sidney S.; Kelly, Henry C.; Denton, Douglas L.; Shore, Sheldon G.

doi:10.1002/9780470132432.ch19

Cited by 23 publications

(8 citation statements)

References 18 publications

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“…[M 2 (CO) 10 ] (M = Mn and Re) and PCy 3 were purchased from Aldrich chemicals and used as received. BH 3 ·thf was synthesized according to the literature procedure . Thin layer chromatography (TLC) was performed on 250 mm diameter aluminum-supported silica gel plates (MERCK TLC Plates).…”

Section: Methodsmentioning

confidence: 99%

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Diborane(6) and Its Analogues Stabilized by Mono-, Bi-, and Trinuclear Group 7 Templates: Combined Experimental and Theoretical Studies

et al. 2020

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Irradiation of [Re2(CO)10] in the presence of BH3·thf resulted in the formation of several rhenium diborane(6) species, for example, [{(OC)4Re}{Re(CO)3}2(μ3-η2:η2:η2-B2H6)(μ-H)], 1; [{(OC)4Re}2{Re(CO)3}(μ3-η2:η2:η1-B2H6)(μ-H)], 2; and [{(OC)4Re}2(μ-η2:η2-B2H6)], 3, comprising diverse coordination modes of the [B2H6]2– ligand. Compound 1 contains a tris(bidentate) [B2H6]2– unit, whereas 2 consists of an unsymmetrically bound [μ3-η2:η2:η1-B2H6]2– ligand. In contrast, the irradiation of [Mn2(CO)10] with BH3·thf yielded only the Mn analogue of 1, [{(OC)4Mn}{Mn(CO)3}2(μ3-η2:η2:η2-B2H6)(μ-H)], 1′. In an attempt to generate the bimetallic Mn-diborane(6), we have carried out the reaction of 1′ with PCy3 under photolytic conditions. The reaction led to the formation of two single base stabilized unsymmetrical diborane(5) species, [{Mn(CO)3}{Mn(CO)2PCy3}(μ-η2:η2-B2H5·PCy3)(μ-H)], 4, and [{Mn(CO)2PCy3}(η3-B2H5·PCy3)], 5. As [B2H6]2– and [B2H5·PCy3]− are isoelectronic, the bondings in 4 and 5 are analogous to that of diborane(6) species 1–3. All the new species have been characterized spectroscopically, and their structures were further confirmed by single-crystal X-ray diffraction studies. DFT-type quantum chemical calculations were carried out that provided insight into the bonding interaction of [B2H6]2– and [B2H5·PCy3]− with the M(CO) n fragments.

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Section: Methodsmentioning

confidence: 99%

“…BH 3 •thf was synthesized according to the literature procedure. 37 Thin layer chromatography (TLC) was performed on 250 mm diameter aluminum-supported silica gel plates (MERCK TLC Plates). The NMR spectra were recorded on 400 or 500 MHz Bruker FT−NMR spectrometer.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Diborane(6) and Its Analogues Stabilized by Mono-, Bi-, and Trinuclear Group 7 Templates: Combined Experimental and Theoretical Studies

et al. 2020

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“…As indicated in previous research, , BH 3 ·THF could be obtained in situ from NaBH 4 and solvated BF 3 . Following the equation in the literature, a converting ability of 6.6 equiv of solvated BF 3 was assumed by adding 5 equiv of NaBH 4 . Within that range, it was reasonable to observe a positive correlation between solvated BF 3 load and the generation of amine-borane 23 , a byproduct formed via amine displacement from tertiary amine 20 and BH 3 ·THF. , Similarly, when the dosage of BF 3 ·THF was fixed at 3.0 equiv, at least 2.25 equiv of NaBH 4 was required for a full conversion of solvated BF 3 .…”

Section: Resultsmentioning

confidence: 96%

“…According to Table , the more BF 3 ·THF (THF = tetrahydrofuran) it charged, the higher percentage of 23 was formed (Table , entries 1–6). As indicated in previous research, , BH 3 ·THF could be obtained in situ from NaBH 4 and solvated BF 3 . Following the equation in the literature, a converting ability of 6.6 equiv of solvated BF 3 was assumed by adding 5 equiv of NaBH 4 .…”

Section: Resultsmentioning

confidence: 99%

Efficient Synthesis of a Key Intermediate for Moxifloxacin Via Intramolecular Double Stereodifferentiation

Liao

Sun

et al. 2022

Org. Process Res. Dev.

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An intramolecular double stereodifferentiation methodology was developed during the synthetic process development of (S,S)-2,8-diazobicylo[4.3.0] nonane (1), the key intermediate of the fourth-generation fluoroquinolone Moxifloxacin. The dual chiral-auxiliary strategy employed in this process guaranteed high stereoselectivity of the hydrogenation reaction to build the cis-[5,6] bicyclic system with desired stereochemistry. 1,6-Bis((R)-1-phenylethyl)-3,4,6,7-tetrahydro-1H-pyrrolo[3,4-b]pyridine-2,5dione (11f), the precursor of the hydrogenation reaction, was prepared from commercially available and affordable chemicals ethyl acetoacetate, (R)-(+)-1-methylbenzylamine, and acryloyl chloride, and the process was further facilitated by telescoping the first three steps into one pot. Moreover, this process has been proven robust at a hectogram scale, providing 450 g of intermediate 1 with a total yield of 56.2% over seven steps and enantiomeric excess of more than 99%, demonstrating the potential for commercial-scale applicability.

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“…borane dimethylsulfide complexes not only from phosphines [85], but also phosphites [86], phosphonites [87] and phosphinites [88]. The borane complexes of trivalent stereogenic phosphorus are most convenient reagents as they are not only easily formed and selectively cleaved, but also are resistant to a variety of reaction conditions [89].…”

Section: Methodsmentioning

confidence: 99%