Zink‐katalysierte Borylierung von primären, sekundären und tertiären Alkylhalogeniden mit Alkoxydiborreagentien bei Raumtemperatur

Bose, Shubhankar Kumar; Fucke, Katharina; Liu, Lei; Steel, Patrick G.; Marder, Todd B.

doi:10.1002/ange.201308855

Cited by 57 publications

(11 citation statements)

References 74 publications

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“…The only experimental report of Zn insertion [15] produced ad ouble-ring insertion of Zn and Bpin, for which the mechanism is evidently different from the general four-step process that is followed by Be, Ba nd SI hydride insertion. It is suggested that the "simple" four-step insertion is unlikely to be observed with Zn hydride,a lthough with carefully selectedc onditions and appropriatelys ubstituted NHCs, one cannote ntirely rule out the possibility of ZnH 2 insertion.…”

Section: Group 12mentioning

confidence: 96%

“…It mayb ep ossible to produce aC do rH gr ing-expanded product such as that reported by Mardera nd co-workers. [15]…”

Section: Group 12mentioning

confidence: 99%

“…[14] An umber of experimental studies, which expand the number and range of cases of insertioni nto NHCs, have subsequently been reported. Marder and co-workers [15] reported the first example of Zn insertion, which arose from attempts to use az inc-chloride adduct of NHC Mes to facilitate the borylation of alkyl halides. Rather,r eaction of NHC-ZnCl 2 with bis(pinacolato)-diboron (B 2 pin 2 )i nt he presence of KOtBu led to the simultaneous activation of two NHC rings resulting in ad ouble-ring expandedp roduct with insertion of zinc into one NHC ring while Bpin was inserted into the secondary NHC ring.…”

Section: Introductionmentioning

confidence: 99%

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Insertion of Group 12–16 Hydrides into NHCs: A Theoretical Investigation

Iversen

Dutton

Wilson

2017

Chemistry An Asian Journal

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Abstract:The endocyclic ring expansiono fN-heterocyclic carbene (NHC) rings by transitionm etal (group 12) and main group (group 13-16) elementh ydrides has been investigated in ac omputational study.I na ddition to previously reported insertion reactivity with Si, B, Be and Zn, similarr eactivity is predicted to be feasible for heavierg roup 13 elements (Al,G a, In, Tl), with the reaction barriersf or Al-Tl calculated to be lower than for boron.I nsertion is not expected with group 15-16 elementh ydrides, as the initial adduct formationist hermodynamically unfavorable. The reaction pathway with group 12 hydrides is calculated to be more favorable with two NHCs rather than as ingle NHC (analogous to Be), however hydride ring insertion with metal dihydrides is not feasible, but ratherareduced NHC is thermodynamically favored. For group 14, ring-insertion reactivityi sp redicted to be feasible with the heavier dihydrides. Trends in reactivity of element hydrides may be related to the protic or hydridic character of the elementhydrides.

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Section: Group 12mentioning

confidence: 96%

“…It mayb ep ossible to produce aC do rH gr ing-expanded product such as that reported by Mardera nd co-workers. [15]…”

Section: Group 12mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Insertion of Group 12–16 Hydrides into NHCs: A Theoretical Investigation

Iversen

Dutton

Wilson

2017

Chemistry An Asian Journal

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“…[4] These more recente xamples involve BÀH, SiÀH, and PÀHb ond activation of molecules such as pinacolborane, phenylsilane,a nd phenylphosphinew ith NHCs or CAACs. [5][6][7][8] Theoretical studies [8] as well as some experimental evidence [6,7] suggest that the important step of the RER following adduct formation is EÀHb ond activation of the element hydride (e.g.,S i-H, [6c] Be-H, [7a,b] or B-H [7c-e] ). [5][6][7][8] Theoretical studies [8] as well as some experimental evidence [6,7] suggest that the important step of the RER following adduct formation is EÀHb ond activation of the element hydride (e.g.,S i-H, [6c] Be-H, [7a,b] or B-H [7c-e] ).…”

mentioning

confidence: 99%

Adduct Formation, B−H Activation and Ring Expansion at Room Temperature from Reactions of HBcat with NHCs

Würtemberger‐Pietsch

Schneider

Marder

et al. 2016

Chemistry A European J

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We report the reactions of catecholborane (HBcat; 1) with unsaturated and saturated NHCs as well as CAAC(Me) . Mono-NHC adducts of the type HBcat⋅NHC (NHC=nPr2 Im, iPr2 Im, iPr2 Im(Me) , and Dipp2 Im) were obtained by stoichiometric reactions of HBcat with the unsaturated NHCs. The reaction of CAAC(Me) with HBcat yielded the B-H activated product CAAC(Me) (H)Bcat via insertion of the carbine-carbon atom into the B-H bond. The saturated NHC Dipp2 SIm reacted in a 2:2 ratio yielding an NHC ring-expanded product at room temperature forming a six-membered -B-C=N-C=C-N- ring via C-N bond cleavage and further migration of the hydrides from two HBcat molecules to the former carbene-carbon atom.

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“…Along with the transformation of the five-membered imidazolin ring into a six-membered metallacycle two hydride substituents migrate from the metal atom to the carbenoid center. [7] For the past few years we have been focusing on the investigation of main group element compounds with the imidazolin-2-iminato ligand. [5] Very recently, a strongly related ring expansion of phosphine-derived NHC attached to 9-BBN hydride was reported.…”

mentioning

confidence: 99%

Systematic Investigation of the Ring‐Expansion Reaction of N‐Heterocyclic Carbenes with an Iminoborane Dihydride

Franz

Inoue

2014

Chemistry An Asian Journal

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Conversions of iminoboranes with an N-heterocyclic carbene (NHC) result in borane dihydride formation (BDF) concomitant with dihydrogenated NHC. The iminoborane dihydrides are prone to a hydride-mediated ring-expansion reaction (RER) at elevated temperature, that is, the insertion of the boron atom into the adjacent CN bond of the NHC to yield boracycles. Upon conversion of a saturated-backbone NHC with respective iminoborane precursors RER yet occurs at ambient temperature to yield the ring-expanded products. When a less bulky iminoborane is brought in contact with sterically unhindered NHC neither the iminoborane dihydride is stable at room temperature nor is the RER observed to take place upon heating. The conversions of iminoboranes with very bulky NHC do not show BDF at ambient temperature and only in the case of the less hindered borane precursor the RER is found to proceed in a controlled fashion upon heating.

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Zink‐katalysierte Borylierung von primären, sekundären und tertiären Alkylhalogeniden mit Alkoxydiborreagentien bei Raumtemperatur

Cited by 57 publications

References 74 publications

Insertion of Group 12–16 Hydrides into NHCs: A Theoretical Investigation

Insertion of Group 12–16 Hydrides into NHCs: A Theoretical Investigation

Adduct Formation, B−H Activation and Ring Expansion at Room Temperature from Reactions of HBcat with NHCs

Systematic Investigation of the Ring‐Expansion Reaction of N‐Heterocyclic Carbenes with an Iminoborane Dihydride

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