stereocontrolled domino reactions · condition, addition of reagents or coupling partners (denmark,...

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Stereocontrolled Domino Reactions

Pellissier, H. Chem. Rev. 2013, 113, 442–524.

Friday Problem Set

Qin Zang 2-8-13

Chem. Soc. Rev., 2009, 38, 3092–3101

2 Definition • Descriptors cascade, domino, tandem, and sequential, are used in the

literature, often seemingly interchangeably and with liberal abandon. (Nicolaou, ACIE 2006, 45, 7134).

• A reaction involving two or more bond-forming transformations that take place under the same reaction conditions, without adding additional reagents and catalysts, and in which the subsequent reactions result as a consequence of the functionality formed by bond formation or fragmentation in the previous step (Tietze, ACIE 1993, 32, 131).

• For this type of transformation also the expression cascade has been used; however, this word does not describe the real meaning and is also used in many ways in science for other phenomena.

• Most domino reactions, as defined by Tietze, fell under the broader category of tandem processes. Other tandem reactions that are not cascades involve the isolation of intermediates, a change in reaction condition, addition of reagents or coupling partners (Denmark, Chem. Rev. 1996, 96, 137).

• Multicomponent reactions should be clearly differentiated from other one-pot processes such as domino, tandem, cascade, or zipper reactions, and in general from all those processes that involve the reaction between two reagents to yield an intermediate which is captured by the successive addition of a new reagent (sequential component reactions (Yus, ACIE 2005, 44, 1602).

3 Tietze’s Classification

Tietze, L. F. Chem. Rev. 1996, 96, 115–136.

1st step 2nd step 3rd step

cationic cationic cationic

anionic anionic anionic

radical radical radical

pericyclic pericyclic pericyclic

photochemical photochemical photochemical

carbenoid carbenoid carbenoid

transition metal-catalyzed transition metal-catalyzed transition metal-catalyzed

oxidation/reduction oxidation/reduction oxidation/reduction

4 Anionic Primary Step: Domino Michael/Dieckmann Reaction

Groth, U.; Kesenheimer, C.; Kreye, P. Synlett 2006, 2223–2226.

(–)-chokol A

5 Question 1: Mechanism

Kinoshita, H.; Osamura, T.; Mizuno, K.; Kinoshita, S.; Iwamura, T.; Watanabe, S.-i.; Kataoka, T.; Muraoka, O.; Tanabe, G. Chem. Eur. J. 2006, 12, 3896–3904.

6 Proposed Mechanism: Domino Thia-Michael/Aldol Reaction


Proposed Mechanism: Diastereoselectivity 7


Proposed Mechanism: Cyclic vs Acyclic Transition State 8


Cationic Sequences: Oxidative Domino Prins/Pinacol Reaction

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Beaulieu, M.-A.; Guérard, K. C.; Maertens, G.; Sabot, C.; Canesi, S. J. Org. Chem. 2011, 76, 9460–9471.

Oxidative Domino Prins/Pinacol Reaction 10

Beaulieu, M.-A.; Guérard, K. C.; Maertens, G.; Sabot, C.; Canesi, S. J. Org. Chem. 2011, 76, 9460–9471.


Lavigne, R. M. A.; Riou, M.; Girardin, M.; Morency, L.; Barriault, L. Org. Lett., 2005, 7, 5921–5923.

Domino Prins/Pinacol Reaction 12


13 Domino Prins/Pinacol Reaction: Mechanism


Domino Reactions Initiated by a Pericyclic Primary Step: Domino Alkylation, Oxy-Cope, Cyclization

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Chen, C.; Layton, M. E.; Sheehan, S. M.; Shair, M. D. J. Am. Chem. Soc. 2000, 122, 7424–7425.

15 Domino Fries rearrangement, Cyclization, Deprotection

Chen, C.; Layton, M. E.; Sheehan, S. M.; Shair, M. D. J. Am. Chem. Soc. 2000, 122, 7424–7425.

(l) TMSOTf, HC(OMe)3, CH2Cl2,-78 to 0 °C


(a) Sauer, E. L. O.; Hooper, J. H.; Woo, T.; Barriault, L. J. Am. Chem. Soc. 2007, 129, 2112–2119. (b) Arns, S.; Barriault, L. Chem. Commun. 2007, 2211–2221.

18 Carbene Sequences: Domino Carbonyl Ylide Formation /1,3-Dipolar Cycloaddition Reaction

Hirata, Y.; Nakamura, S.; Watanabe, N.; Kataoka, O.; Kurrosaki, Anada, M.; Kitagaki, S.; Shiro, M.; Hashimoto, S. Chem. Eur. J. 2006, 12, 8898–8925.

19 Question 4: Product and Mechanism

Muroni, D.; Mucedda, M.; Saba, A. Tetrahedron: Asymmetry 2009, 20, 1154–1159.

20 Question 4: Product and Mechanism

Muroni, D.; Mucedda, M.; Saba, A. Tetrahedron: Asymmetry 2009, 20, 1154–1159.

Transition-metal-catalyzed Domino Reactions: Domino Metathesis Reaction

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Schubert, M.; Metz, P. Angew. Chem., Int. Ed. 2011, 50, 2954–2956.

22

Gibbs, R. A.; Okamura, W. H. J. Am. Chem. Soc. 1988, 110, 4062–4063.

Domino [2,3] Rearrangement, Diels-Alder Reaction

Question 5: Mechanism 23

Iglesias, B.; Torrado, A.; de Lera, A. R. J. Org. Chem. 2000, 65, 2696–2705.

Question 5: Mechanism 24

Iglesias, B.; Torrado, A.; de Lera, A. R. J. Org. Chem. 2000, 65, 2696–2705.

Domino Reactions Initiated by an Oxidation 26

Peed, J.; Davies, I. R.; Peacock, L. R.; Taylor, J. E.; Kociok-Köhn, G.; Bull, S. D. J. Org. Chem. 2012, 77, 543–555.

Domino Reactions Initiated by a Ring-Opening Reaction 27

Fujioka, H.; Matsuda, S.; Horai, M.; Fujii, E.; Morishita, M.; Nishiguchi, N.; Hata, K.; Kita, Y. Chem. Eur. J. 2007, 13, 5238–5248.

28 Multicomponent Reactions Domino Michael/Aldol/Retro-Dieckmann Reaction

Coquerel, Y.; Filippini, M.-H.; Bensa, D.; Rodriguez, J. Chem. Eur. J. 2008, 14, 3078.

stereocontrolled domino reactions · condition, addition of reagents or coupling partners (denmark,...

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