A Convenient Method for the Generation of Allylic Dihaloboranes and Diallyl(chloro)borane and Their Application in the Allylboration of Alkenes and Acetylenes

Bubnov, Yurii N.; Kuznetsov, N. Yu.; Pastukhov, F. V.; Kublitsky, Vadim V.

doi:10.1002/ejoc.200500391

Cited by 30 publications

(11 citation statements)

References 25 publications

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“…39 Thus haloboration of olefins is an uncommon route to b-haloalkylboranes with only one inter-and one intramolecular synthesis reported to our knowledge. 40,41 Other methods are preferred to prepare this versatile structural motif. 42 While isolated olefins do not undergo haloboration, Lappert et al showed that allenes reacted smoothly at À20 1C with BBr 3 to give the respective 1,2 adduct.…”

Section: Haloboration Of Cq Q Qc Double Bondsmentioning

confidence: 99%

Haloboration: scope, mechanism and utility

2021

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Section: Haloboration Of Cq Q Qc Double Bondsmentioning

confidence: 99%

Haloboration: scope, mechanism and utility

2021

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“…The synthesis of BN-9,1-Naph commences with the commercially available 2-vinylpyridine 1 that reacts with the in situ generated allylboron dichloride to give adduct 2 . Without further purification, compound 2 in the presence of Grubbs’ first generation metathesis catalyst produces the ring-closed compound 3 in good yield over two steps.…”

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confidence: 99%

“…The synthesis of BN-9,1-Naph commences with the commercially available 2-vinylpyridine 1 that reacts with the in situ generated allylboron dichloride 12 Unfortunately, the crystal structure of the parent BN-9,1-Naph is disordered. However, single-crystal X-ray analysis of fluorine-substituted 7F-BN-9,1-Naph (prepared using the same synthetic route, Scheme 1) unambiguously established the connectivity of the BN-9,1-Naph core (Scheme 1, bottom right ORTEP illustration).…”

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The Least Stable Isomer of BN Naphthalene: Toward Predictive Trends for the Optoelectronic Properties of BN Acenes

et al. 2017

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The least stable isomer of the parental BN naphthalene series has been synthesized in a simple four-step sequence. Its experimental electronic structure characterization via UV-PES, cyclic voltammetry, and UV-vis spectroscopy in direct comparison with three other known BN naphthalene isomers has established two guiding principles for predicting the electronic structures of BN acene compounds: (1) Orientational BN isomers have similar HOMO-LUMO gaps. (2) For each pair of orientational BN isomers, the more thermodynamically stable compound has the lower HOMO energy. Furthermore, we demonstrate that BN/CC isosterism in the context of BN-9,1-Naph can impact crystal packing to favor a cofacial π-stack motif.

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“…Only one set of signals was observed in the 1 H, 11 B, and 119 Sn NMR spectra of (S p )-2-(+)-MPE, confirming the selective conversion of only one of the enantiomers of 1-OMe to form a single diastereomer of the chelate complex. To determine the stereochemical configuration at boron, we acquired 2D-NOESY 1 H NMR spectroscopy data.…”

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confidence: 68%

“…[8,9] We converted 1-Cl to the methoxy derivative 1,2-Fc(BMe(OMe))-(SnMe 2 Cl) (1-OMe) and treated the latter with 0.5 equivalents of (1R,2R)-(À)-N-methylpseudoephedrine ((À)-MPE) or (1S,2S)-(+)-N-methylpseudoephedrine ((+)-MPE, Scheme 1). [10,11] The crude product was extracted with hexanes, and the chelate complexes (R p )-2-(À)-MPE and (S p )-2-(+)-MPE were isolated from the corresponding solid fractions; the characteristics of the (S p )-2-(+)-MPE enantiomer are described below, and similar considerations apply to the R p isomer.…”

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Allylation of Ketones with a Ferrocene‐Based Planar Chiral Lewis Acid

2008

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-N-methyl pseudoephedrine, and (4S,5S)-(-)-4,5-dihydro-4-methoxymethyl-2-methyl-5-phenyloxazole) were purchased from Sigma Aldrich and dichlorophenylborane from Acros. All chemicals were used without further purification. (1R,2R)-(-)-N-methyl pseudoephedrine [1] , Me 3 SnAll [2] , and 1,2-Fc(SnMe 2 Cl)(BClMe) [3] were prepared according to literature procedures. Deuterated chloroform (CDCl 3 >99.7%) was obtained from Cambridge Isotope Laboratories (CIL). The solvent was stirred for several days over anhydrous CaH 2 , then degassed via several freeze pump thaw cycles and stored over 3Å molecular sieves. All reactions and manipulations were carried out under an atmosphere of prepurified nitrogen using either Schlenk techniques or an inert-atmosphere glove box (MBraun Glovebox Technology). Hydrocarbon and chlorinated solvents were purified using a solvent purification system (Innovative Technologies; alumina / copper columns for hydrocarbon solvents) and the chlorinated solvents were subsequently degassed via several freeze pump thaw cycles.All 499.9 MHz 1 H, 125.7 MHz 13 C, 186.4 MHz 119 Sn, and 160.3 11 B NMR spectra were recorded on a Varian INOVA NMR spectrometer (Varian Inc., Palo Alto, CA) equipped with a 5 mm dual broadband gradient probe (Nalorac, Varian Inc., Martinez, CA). Solution 1 H and 13 C NMR spectra were referenced internally to the solvent signals. 119 Sn and 11 B NMR spectra were referenced externally to SnMe 4 (δ = 0) and BF 3 . Et 2 O (δ = 0) in C 6 D 6 , respectively. Splittings of NMR signals are abbreviated as pst (pseudo-triplet), dpst (doublet of pseudo-triplet), nr (not resolved).Two-dimensional 1 H NOESY [4] measurements were obtained with the standard pulse sequence that was followed by a 90° pulse flanked by two 5 G/cm gradient for dephasing any residual transverse magnetization and suppressing potential artifacts, before the relaxation delay. Spectra were recorded in the phase sensitive mode by employing the TPPI improvement [5] of the States-Haberkorn-Ruben Hypercomplex method. [6] Typically, 256 t1 increments of 2K complex data points over 5.0 kHz spectral widths were collected with 32 scans per t1 increment, preceded by 16 or 32 dummy scans, and a relaxation delay of 2 s. Data sets were processed on a Sun Blade 100 workstation (Sun Microsystems Inc., Palo Alto, CA) using the VNMR software package (Varian Inc., Palo Alto, CA). In order to decrease t1 ridges arising from incorrect treatment of the first data point in the discreet Fourier transform (FT) algorithm, the spectrum corresponding to the first t1 value was divided by 2 prior to FT along t1. [7] Unshifted Sine Bell window functions were used in both dimensions. Data sets were zero-filled in the t1 dimension yielding 1K x 1K final matrices.Elemental analyses were performed by Quantitative Technologies Inc. Whitehouse, NJ. Optical rotation analysis was performed on an Autopol II polarimeter, Rudolph Research Analytical, using a tungsten-halogen light source operating at λ = 589 nm. GC analysis was performed on Hewlett Packard ...

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A Convenient Method for the Generation of Allylic Dihaloboranes and Diallyl(chloro)borane and Their Application in the Allylboration of Alkenes and Acetylenes

Cited by 30 publications

References 25 publications

Haloboration: scope, mechanism and utility

Haloboration: scope, mechanism and utility

The Least Stable Isomer of BN Naphthalene: Toward Predictive Trends for the Optoelectronic Properties of BN Acenes

Allylation of Ketones with a Ferrocene‐Based Planar Chiral Lewis Acid

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