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. 2017 Sep;49(18):4229-4246.
doi: 10.1055/s-0036-1589054. Epub 2017 Jul 25.

Lewis Acid Mediated Cyclizations: Diastereoselective Synthesis of Six- to Eight-Membered Substituted Cyclic Ethers

Arun K Ghosh  1   2 , Anthony J Tomaine  1 , Kelsey E Cantwell  1
Affiliations

Lewis Acid Mediated Cyclizations: Diastereoselective Synthesis of Six- to Eight-Membered Substituted Cyclic Ethers

Arun K Ghosh et al. Synthesis (Stuttg). 2017 Sep.

Abstract

Cyclic ethers are widely abundant in natural products. Cyclic ether templates are also utilized in drug design and medicinal chemistry. Although the synthetic processes for this class of compounds have been studied extensively with respect to five- and six-membered rings, medium-sized cyclic ethers are synthetically more challenging due to a variety of factors. Herein, we report our results on the Lewis acid catalyzed synthesis of medium-sized cyclic ethers in a diastereoselective manner.

Keywords: Lewis acids; cyclic ethers; cyclization; diastereoselectivity; oxacycles; oxepanes; oxocenes; polycycles.

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Figures

Figure 1
Figure 1
Structures of oxacyclic bioactive molecules
Figure 2
Figure 2
NOE correlations of oxepine derivative 35
Figure 3
Figure 3
NOE correlations of oxepane derivative 45
Scheme 1
Scheme 1
Synthesis of tetrahydropyrans by Hosomi and Loh and their co-workers
Scheme 2
Scheme 2
Tetrahydropyran synthesis by Ghosh and Nicponski
Scheme 3
Scheme 3
Polycyclic ring formations by Ghosh and co-workers
Scheme 4
Scheme 4
Formation of oxocene product as a minor isomer, with benzyloxyacetaldehyde
Scheme 5
Scheme 5
Oxocene synthesis by Overman and co-workers
Scheme 6
Scheme 6
Preparation of exo-oxacyclic isomer 31k
Scheme 7
Scheme 7
Transition-state analysis for the oxepine products
Scheme 8
Scheme 8
TMSOTf-catalyzed isomerization of alkenol 44
Scheme 9
Scheme 9
X-ray crystal structure determination of 48 (white = hydrogen, black = carbon, red = oxygen, blue = nitrogen, yellow = sulfur, brown = bromine)
Scheme 10
Scheme 10
Transition-state analysis for the oxepane products
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