Recent advances in transition-metal-catalyzed intermolecular carbomagnesiation and carbozincation

Kei Murakami and
Hideki Yorimitsu

Review
Published 11 Feb 2013

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1. Graphical Abstract
2. Scheme 1: Variation of substrates for carbomagnesiation and carbozincation in this article.
  
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3. Scheme 2: Copper-catalyzed arylmagnesiation and allylmagnesiation of alkynyl sulfone.
  
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4. Scheme 3: Copper-catalyzed four-component reaction of alkynyl sulfoxide with alkylzinc reagent, diiodomethane...
  
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5. Scheme 4: Rhodium-catalyzed reaction of aryl alkynyl ketones with arylzinc reagents.
  
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6. Scheme 5: Allylmagnesiation of propargyl alcohol, which provides the anti-addition product.
  
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7. Scheme 6: Negishi’s total synthesis of (Z)-γ-bisabolene by allylmagnesiation.
  
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8. Scheme 7: Iron-catalyzed syn-carbomagnesiation of propargylic or homopropargylic alcohol.
  
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9. Scheme 8: Mechanism of iron-catalyzed carbomagnesiation.
  
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10. Scheme 9: Regio- and stereoselective manganese-catalyzed allylmagnesiation.
  
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11. Scheme 10: Vinylation and alkylation of arylacetylene-bearing hydroxy group.
  
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12. Scheme 11: Arylmagnesiation of (2-pyridyl)silyl-substituted alkynes.
  
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13. Scheme 12: Synthesis of tamoxifen from 2g.
  
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14. Scheme 13: Controlling regioselectivity of carbocupration by attaching directing groups.
  
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15. Scheme 14: Rhodium-catalyzed carbozincation of ynamides.
  
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16. Scheme 15: Synthesis of 4-pentenenitriles through carbometalation followed by aza-Claisen rearrangement.
  
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17. Scheme 16: Uncatalyzed carbomagnesiation of cyclopropenes.
  
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18. Scheme 17: Iron-catalyzed carbometalation of cyclopropenes.
  
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19. Scheme 18: Enantioselective carbozincation of cyclopropenes.
  
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20. Scheme 19: Copper-catalyzed facially selective carbomagnesiation.
  
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21. Scheme 20: Arylmagnesiation of cyclopropenes.
  
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22. Scheme 21: Enantioselective methylmagnesiation of cyclopropenes without catalyst.
  
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23. Scheme 22: Copper-catalyzed carbozincation.
  
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24. Scheme 23: Enantioselective ethylzincation of cyclopropenes.
  
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25. Scheme 24: Nickel-catalyzed ring-opening aryl- and alkenylmagnesiation of a methylenecyclopropane.
  
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26. Scheme 25: Reaction mechanism.
  
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27. Scheme 26: Nickel-catalyzed carbomagnesiation of arylacetylene and dialkylacetylene.
  
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28. Scheme 27: Nickel-catalyzed carbozincation of arylacetylenes and its application to the synthesis of tamoxifen....
  
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29. Scheme 28: Bristol-Myers Squibb’s nickel-catalyzed phenylzincation.
  
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30. Scheme 29: Iron/NHC-catalyzed arylmagnesiation of aryl(alkyl)acetylene.
  
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31. Scheme 30: Iron/copper-cocatalyzed alkylmagnesiation of aryl(alkyl)acetylenes.
  
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32. Scheme 31: Iron-catalyzed hydrometalation.
  
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33. Scheme 32: Iron/copper-cocatalyzed arylmagnesiation of dialkylacetylenes.
  
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34. Scheme 33: Chromium-catalyzed arylmagnesiation of alkynes.
  
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35. Scheme 34: Cobalt-catalyzed arylzincation of alkynes.
  
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36. Scheme 35: Cobalt-catalyzed formation of arylzinc reagents and subsequent arylzincation of alkynes.
  
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37. Scheme 36: Cobalt-catalyzed benzylzincation of dialkylacetylene and aryl(alkyl)acetylenes.
  
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38. Scheme 37: Synthesis of estrogen receptor antagonist.
  
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39. Scheme 38: Cobalt-catalyzed allylzincation of aryl-substituted alkynes.
  
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40. Scheme 39: Silver-catalyzed alkylmagnesiation of terminal alkyne.
  
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41. Scheme 40: Proposed mechanism of silver-catalyzed alkylmagnesiation.
  
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42. Scheme 41: Zirconium-catalyzed ethylzincation of terminal alkenes.
  
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43. Scheme 42: Zirconium-catalyzed alkylmagnesiation.
  
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44. Scheme 43: Titanium-catalyzed carbomagnesiation.
  
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45. Scheme 44: Three-component coupling reaction.
  
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46. Scheme 45: Iron-catalyzed arylzincation reaction of oxabicyclic alkenes.
  
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47. Scheme 46: Reaction of allenyl ketones with organomagnesium reagent.
  
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48. Scheme 47: Regio- and stereoselective reaction of a 2,3-allenoate.
  
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49. Scheme 48: Three-component coupling reaction of 1,2-allenoate, organozinc reagent, and ketone.
  
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50. Scheme 49: Proposed mechanism for a rhodium-catalyzed arylzincation of allenes.
  
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51. Scheme 50: Synthesis of skipped polyenes by iterative arylzincation/allenylation reaction.
  
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52. Scheme 51: Synthesis of 1,4-diorganomagnesium compound from 1,2-dienes.
  
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53. Scheme 52: Synthesis of tricyclic compounds.
  
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54. Scheme 53: Manganese-catalyzed allylmagnesiation of allenes.
  
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55. Scheme 54: Copper-catalyzed alkylmagnesiation of 1,3-dienes and 1,3-enynes.
  
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56. Scheme 55: Chromium-catalyzed methallylmagnesiation of 1,6-diynes.
  
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57. Scheme 56: Chromium-catalyzed allylmagnesiation of 1,6-enynes.
  
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58. Scheme 57: Proposed mechanism of the chromium-catalyzed methallylmagnesiation.
  
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Beilstein J. Org. Chem. 2013, 9, 278–302, doi:10.3762/bjoc.9.34

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Recent advances in transition-metal-catalyzed intermolecular carbomagnesiation and carbozincation

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