Desymmetrization of Prochiral Diaryl Sulfoxides by an Asymmetric Sulfoxide–Magnesium Exchange

Hampel, Thomas; Ruppenthal, Simon; Sälinger, Daniel; Brückner, Reinhard

doi:10.1002/chem.201103928

Cited by 16 publications

(25 citation statements)

References 101 publications

(76 reference statements)

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“…This was (1) in spite of their symmetry and thus (2) by desymmetrizing them. Being the first reactions of their kind these sulfinylations succeeded in up to 100 % yield with up to 97 % ee …”

Section: Literature Sulfinylations Of Organozinc Compoundsmentioning

confidence: 99%

“…In contrast, we prepared alkyl aryl sulfoxides – including ethyl phenyl sulfoxide ( 9a ) – and alkyl heteroaryl sulfoxides[12c] asymmetrically : by sulfinylating dialkylmagnesium compounds with symmetric (!) diaryl[12a], [12b] or diheteroaryl sulfoxides. [12c] Asymmetry arose from adding Li 2 ‐( S )‐BINOLate .…”

Section: Literature Sulfinylations Of Organozinc Compoundsmentioning

confidence: 99%

“…diaryl[12a], [12b] or diheteroaryl sulfoxides. [12c] Asymmetry arose from adding Li 2 ‐( S )‐BINOLate . Its involvement led to the transfer of uniquely configured arylsulfinyl groups or heteroarylsulfinyl groups from the respective sulfoxides.…”

Section: Literature Sulfinylations Of Organozinc Compoundsmentioning

confidence: 99%

“…Sulfoxide (–)‐ 9a is ( S )‐configured according to a previous study. [12b] As a consequence, sulfoxide (+)‐ 9a must be ( R )‐configured. The configuration of the major enantiomer of all specimens of sulfoxide 9a resulting from the experiments tabulated here was deduced from its migratory aptitude on a Chiralcel OD‐3 column in n ‐heptane/ i PrOH (96:4) (cf.…”

Section: Asymmetric Arylsulfinylations Of “Activated Diethylzinc”mentioning

confidence: 99%

“…for (–)‐ 51 and ref. [12b] for (–)‐ 48 and (–)‐ 52 ]. The absolute configuration of 4‐chlorophenyl hexyl sulfoxide [(–)‐ 53 ] was determined after converting it through sulfoxide–magnesium exchange with PhMgBr – with inversion of configuration – into dextrorotatory hexyl phenyl sulfoxide.…”

Section: Arylsulfinylations Of Activated Dialkylzinc Compounds Other mentioning

confidence: 99%

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Asymmetric Sulfinylations ofN‐Methylephedrine‐Modified Tri‐ or Tetraalkyl Zincates by Symmetric Diaryl Sulfoxides

Ruppenthal

Brückner

2018

Eur J Org Chem

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Diethylzinc was treated with 1 or 2 equiv. of AlkMgCl or PhMgBr (preferably) or with 1 equiv. of nBuLi (less efficiently) for forming species – plausibly zincates – which were sulfinylated by diaryl sulfoxides to give racemic alkyl aryl sulfoxides in yields reaching 100 %. Dialkylzinc reagents were also activated by treatments with 1 or 2 equiv. of an enantiomerically pure alkylmagnesium β‐aminoalkoxide. This worked best when the alkoxide stemmed from a dialkylmagnesium reagent and an equimolar amount of N‐methyl‐(–)‐ephedrine. This second activation mode allowed sulfinylations of what was originally the dialkylzinc reagent with diaryl sulfoxides. This generated alkyl aryl sulfoxides with enantiomeric ratios up to 93:7 in up to 100 % yield.

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Section: Literature Sulfinylations Of Organozinc Compoundsmentioning

confidence: 99%

Section: Literature Sulfinylations Of Organozinc Compoundsmentioning

confidence: 99%

Section: Literature Sulfinylations Of Organozinc Compoundsmentioning

confidence: 99%

Section: Asymmetric Arylsulfinylations Of “Activated Diethylzinc”mentioning

confidence: 99%

Section: Arylsulfinylations Of Activated Dialkylzinc Compounds Other mentioning

confidence: 99%

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Asymmetric Sulfinylations ofN‐Methylephedrine‐Modified Tri‐ or Tetraalkyl Zincates by Symmetric Diaryl Sulfoxides

Ruppenthal

Brückner

2018

Eur J Org Chem

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TADF Invariant of Host Polarity and Ultralong Fluorescence Lifetimes in a Donor‐Acceptor Emitter Featuring a Hybrid Sulfone‐Triarylboron Acceptor**

et al. 2023

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e][1,4]thiaborinine 5,5-dioxide (SO2B)-a high triplet (T 1 = 3.05 eV) strongly electron-accepting boracycle was successfully utilised in thermally activated delayed fluorescence (TADF) emitters PXZ-Dipp-SO2B and CZ-Dipp-SO2B. We demonstrate the near-complete separation of highest occupied and lowest unoccupied molecular orbitals leading to a low oscillator strength of the S 1 !S 0 CT transition, resulting in very long ca. 83 ns and 400 ns prompt fluorescence lifetimes for CZ-Dipp-SO2B and PXZ-Dipp-SO2B, respectively, but retaining near unity photoluminescence quantum yield. OLEDs using CZ-Dipp-SO2B as the luminescent dopant display high external quantum efficiency (EQE) of 23.3 % and maximum luminance of 18600 cd m À 2 with low efficiency roll off at high brightness. For CZ-Dipp-SO2B, reverse intersystem crossing (rISC) is mediated through the vibronic coupling of two charge transfer (CT) states, without involving the triplet local excited state ( 3 LE), resulting in remarkable rISC rate invariance to environmental polarity and polarisability whilst giving high organic light-emitting diode (OLED) efficiency. This new form of rISC allows stable OLED performance to be achieved in different host environments.

show abstract

TADF Invariant of Host Polarity and Ultralong Fluorescence Lifetimes in a Donor‐Acceptor Emitter Featuring a Hybrid Sulfone‐Triarylboron Acceptor**

et al. 2023

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10H‐Dibenzo[b,e][1,4]thiaborinine 5,5‐dioxide (SO2B)—a high triplet (T1=3.05 eV) strongly electron‐accepting boracycle was successfully utilised in thermally activated delayed fluorescence (TADF) emitters PXZ‐Dipp‐SO2B and CZ‐Dipp‐SO2B. We demonstrate the near‐complete separation of highest occupied and lowest unoccupied molecular orbitals leading to a low oscillator strength of the S1→S0 CT transition, resulting in very long ca. 83 ns and 400 ns prompt fluorescence lifetimes for CZ‐Dipp‐SO2B and PXZ‐Dipp‐SO2B, respectively, but retaining near unity photoluminescence quantum yield. OLEDs using CZ‐Dipp‐SO2B as the luminescent dopant display high external quantum efficiency (EQE) of 23.3 % and maximum luminance of 18600 cd m−2 with low efficiency roll off at high brightness. For CZ‐Dipp‐SO2B, reverse intersystem crossing (rISC) is mediated through the vibronic coupling of two charge transfer (CT) states, without involving the triplet local excited state (3LE), resulting in remarkable rISC rate invariance to environmental polarity and polarisability whilst giving high organic light‐emitting diode (OLED) efficiency. This new form of rISC allows stable OLED performance to be achieved in different host environments.

show abstract

Desymmetrization of Prochiral Diaryl Sulfoxides by an Asymmetric Sulfoxide–Magnesium Exchange

Cited by 16 publications

References 101 publications

Asymmetric Sulfinylations ofN‐Methylephedrine‐Modified Tri‐ or Tetraalkyl Zincates by Symmetric Diaryl Sulfoxides

Asymmetric Sulfinylations ofN‐Methylephedrine‐Modified Tri‐ or Tetraalkyl Zincates by Symmetric Diaryl Sulfoxides

TADF Invariant of Host Polarity and Ultralong Fluorescence Lifetimes in a Donor‐Acceptor Emitter Featuring a Hybrid Sulfone‐Triarylboron Acceptor**

TADF Invariant of Host Polarity and Ultralong Fluorescence Lifetimes in a Donor‐Acceptor Emitter Featuring a Hybrid Sulfone‐Triarylboron Acceptor**

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