References
But let's clear some things up.
The rhodium-catalyzed O–H insertion is, in fact, very real! You can check out the paper yourself! But we may have portrayed it in comedically exaggerated fashion. But what can I say; that's show business for you! There is much more research exploring it right now. Gong and colleagues cite a review by Ye and McKervey for the rhodium(II)-catalyzed O–H insertion reaction. The following citation index summarizes their review and details current, relevant research that cites Ye and McKervey. Check it out!
Ye, T.; McKervey, M. A. Chem. Rev. 1994, 94, 1091.
Ye and McKervey review organic syntheses with α-diazocarbonyl compounds, whose diazo groups are liberated by catalyst to insert new bonds in their place. A multitude of reaction pathways and derivatives are possible, including substitutions, bond insertions, ring formations, and more, facilitated by a multitude of catalysts. Scheme 22 shows many possible derivatives of diazocarbonyls.
The review focuses, in one part, on α-α-substitutions catalyzed by heavy metals, including copper, nickel, palladium, and especially rhodium. Due to their diversity and favorable conditions, these reactions can replace Wolff rearrangements for bond insertions entirely, and, in doing so, greatly expand the applications of diazocarbonyls. Ye and McKervey specifically discuss rhodium(II) acetate-catalyzed O–H insertions at low catalyst concentrations in room temperature, such as that in Scheme 39.
Paulissen, R.; Reimlinger, H.; Hayez, E.; Hubert, A. J.; Teyssil, Ph. Tetrahedron Lett. 1973, 14, 2233.
Noels, A. F.; Petiniot, D. N.; Hubert, A. J.; Teyssi B, Ph. Tetrahedron 1982, 38, 2733.
In these reactions, rhodium(II) acetate inserts itself into the compound, liberating nitrogen, which allows attack by OH-containing compounds; after the attack, the catalyst is liberated and regenerated, completing the reaction. Mechanistically, this is virtually identical to the reaction utilized to afford 4 by Gong and colleagues in the synthesis of maeocrystal V.
The following publications cite Ye and McKervey:
The following publications cite Ye and McKervey:
1) Jindal, G.; Kisan, H. K.; Sunoj, R. B. ACS Catal. 2015, 5, 480-503.
Jindal and colleagues discuss an important class of transition metal catalysts that are used in conjunction with other catalysts under multicatalytic conditons: dirhodium carboxylates. The insertion of dirhodium carbenoids to C–X bonds (X = N, O, S) offers diverse synthetic targets, which are explored in the Ye and McKervey paper (shown above).
Example Reaction:
2) Bosnidou, A.-E.; Kalpogiannaki, D.; Karanestora, S.; Nixas, J. A.; Hadjiarapoglou, L. P. J. Org. Chem. 2015, 80, 1279-1283.
Bosnidou and colleagues demonstrate that metal-catalyzed decomposition reactions of α-diazocarbonyl compounds are useful to generate metal carbenoids, which lead to useful transformations such as X–H bond insertion. Furthermore, using iodonium ylides in this type of chemistry is complementary to that of diazo compounds without hazard. Ye and McKervey discussed this reaction in Chem. Rev., and Bosnidou and colleagues build off of it with other methods such as photochemical activations.
Example Reaction Pathway:
3) Ying, X.; Zhen, L.; Feng, S.; Zhang, Y.; Wang, J. J. Org. Chem. 2015, 80, 223-236.
Ying and colleagues explain that transition-metal catalyzed C–H functionalization with carbene species is unique and very practical in organic synthesis. The most notable example is Rh(II) carbine C–H bond insertion reactions, not unlike those discussed by Ye and McKervey. Ying and colleagues also wish to show a new approach to this classic scheme by using cat Ir(III) with diazo compounds and aromatic structures as starting materials.
Their general reaction scheme:
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