Metal-free visible-light-mediated aerobic oxidation of silanes to silanols

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SCIENCE CHINA Chemistry, Volume 61, Issue 12: 1594-1599(2018) https://doi.org/10.1007/s11426-018-9289-9

Metal-free visible-light-mediated aerobic oxidation of silanes to silanols

Jing Wang, Bin Li, Li-Chuan Liu, Chenran Jiang, Tao He, Wei He*
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  • ReceivedMay 3, 2018
  • AcceptedMay 21, 2018
  • PublishedAug 2, 2018
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Abstract

Oxidation of silanes into silanols using water/air has attracted considerable attention. The known methods with no exception required a metal catalyst. Herein we report the first metal-free method: 2 mol% Rose Bengal as the catalyst, air (O2) as the oxidant, water as the additive and under visible light irradiation. While this method produces various silanols in a simple, cost-effective, efficient (92%–99% yields) and scalable fashion, its reaction mechanism is very different than the reported ones associated with metal catalysis.


Funded by

the National Key R&D Program of China(2017YFA0505200)

the National Natural Science Foundation of China(21625104,21521091)


Acknowledgment

This work was supported by the National Key R&D Program of China (2017YFA0505200) and the National Natural Science Foundation of China (21625104, 21521091).


Interest statement

The authors declare that they have no conflict of interest.


Supplement

Supporting Information

The supporting information is available online at http://chem.scichina.com and http://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.


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  • Click to view Download high-quality image

    Figure 1

    Proposed reaction mechanism (color online).

  • Click to view Download high-quality image

    Scheme 1

    Synthetic methods for silanols (color online).

  • Click to view Download high-quality image

    Scheme 2

    Controlled Experiments to Verify 1O2 (color online).

  • Table 1   Table 1 Optimization of reaction conditionsa)

    Entry

    Catalyst

    Solvent

    Oxidants

    Conversion/Yield (%)b)

    1

    Rose Bengal

    THF

    Air

    70/67

    2

    Rose Bengal

    THF

    Air/H2O

    >99/98

    3

    Eosin B

    THF

    Air/H2O

    <5/–

    4

    Eosin Y

    THF

    Air/H2O

    <5/–

    5

    Fluorescein

    THF

    Air/H2O

    <5/–

    6

    –

    THF

    Air/H2O

    <5/–

    7c)

    Rose Bengal

    THF

    Air/H2O

    <5/–

    8d)

    Rose Bengal

    THF

    Air/H2O

    >99/97

    9e)

    Rose Bengal

    THF

    Air/H2O

    >99/95

    10f)

    Rose Bengal

    THF

    Air/H2O

    47/43

    11

    Rose Bengal

    DME

    Air/H2O

    90/86

    12

    Rose Bengal

    DMF

    Air/H2O

    50/47

    13

    Rose Bengal

    DMA

    Air/H2O

    13/10

    14

    Rose Bengal

    MeCN

    Air/H2O

    <5/–

    15g)

    Rose Bengal

    MeOH

    Air/H2O

    60/53

    16

    Rose Bengal

    Acetone

    Air/H2O

    77/72

    17

    Rose Bengal

    DMSO

    Air/H2O

    55/51

    18

    Rose Bengal

    THF

    N2/H2O

    <5/–

    19

    Rose Bengal

    Dry THF

    O2

    90/86h)

    20

    Rose Bengal

    Dry THF

    O2/H2O

    >99/97

    Reaction conditions unless otherwise stated: triphenysilane 1a (0.4?mmol), H2O (50?μL), photocatalyst (2 mol%), otherwise noted, solvent (2?mL) without anhydrous treatment, using a 200?W white LED as the visible light source, 12?h. b) Yields after chromatography. c) Reaction performed in dark. d) 5 mol%, e) 10 mol% and f) 100 mol% catalyst was used, respectively. g) Alcoholysis product was isolated. h) The reaction time was 72?h.

  • Table 2   Table 2 Substrate scope of the organocatalytic oxidation of silane a,b)

    2a

    2b

    2c

    2d

    98% (12?h)

    78% (12?h)

    97% (12?h)

    99% (12?h)

    99% (gram scale)

    95% (24?h)

    ?

    2e

    2f

    2g

    2h

    97% (12?h)

    92% (12?h)

    97% (12?h)

    99% (12?h)

    2i

    2j

    2k

    2m

    81% (12?h)

    98% (12?h)

    98% (12?h)

    97% (12?h)

    97% (24?h)

    ?

    Standard conditions unless otherwise stated: silane (0.4?mmol), Rose Bengal (2.0 mol%), H2O (50?μL),THF (2?mL), 200?W white LED, air, r.t., 12?h or 24?h. b) Isolated yields.

  • Table 3   Table 3 Controlled Experiments of Reaction with H218O and 16O2a)

    Entry

    Time (h)

    Conversion

    (%)

    Ph3Si18OH

    in 2a (%)b)

    Ph3Si16OH

    in 2a (%)b)

    1

    0.3

    2.7

    33

    67

    2

    1

    5.8

    66

    34

    3

    6

    71.5

    65

    35

    4

    12

    100

    67

    33

    Reaction conditions: triphenysilane 1a(0.4?mmol), H218O (50?μL), Rose Bengal (2 mol%), dry THF (2?mL), 200?W white LED, reacting in a freshly dried Schlenk tube under the 16O2 atmosphere. b) The relative amount of Ph3Si18OH and Ph3Si16OH in 2a was analyzed by GC-MS.

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