What Is Burgess Dehydrating Agent?
Burgess reagent [methyl N-(triethylaminosulfonyl)carbamate] is a neutral, white crystalline solid that can be used to effectively generate olefins from secondary and tertiary alcohols. Burgess reagent is a powerful dehydrating agent for secondary and tertiary alcohols and can be dehydrated under mild conditions. However, since the reagent is sensitive to air and moisture and has a short half-life, it is advisable to use a freshly prepared reagent, which can be prepared by reacting chlorosulfonyl isocyanate with triethylamine in methanol [1]. Wipf developed a polymer-loaded Burgess dehydrating agent [2] with improved stability.
Fig 1. Synthesis and improvement of Burgess reagent.
Reaction Mechanism of Burgess Dehydration
The reaction mechanism of Burgess dehydration is that the hydroxyl group attacks the sulfur, followed by cis elimination.
Fig 2. Mechanism of Burgess dehydration. [1]
Application Examples of Burgess Reagent
- Example 1: The primary use of Burgess reagent is to dehydrate secondary and tertiary alcohols to form olefins. Alcohols are dehydrated to form olefins in the absence of other groups. For example, in the total synthesis of the natural product (+)-narciclasine, Rigby synthesized an advanced synthetic intermediate (example 1) by using a dehydrating agent [3]. This method was also used by Nicolaou for the synthesis of efrotomyein, by Uskokovic for the synthesis of pravastatin, and by Holton for the synthesis of Taxol.
- Example 2: Burgess reagent can also be used to synthesize isonitriles from formamides, compounds from primary amides, nitrile oxides from nitroalkanes, nitriles from oxime, and carbamates from primary alcohol. For example, in the last step of the total synthesis of the natural products welwitindolinone A and fischerindoles I and G, the synthesis of isocyanide was achieved by using Burgess reagent (example 2) [4].
- Example 3: In recent years, Burgess reagent has been used more frequently for the dehydration cyclization of hydroxyamides or hydroxysulfamides. For example, in the total synthesis of the antibiotic (-)-Madumycin Ⅰ, Meyers used Burgess reagent to construct the oxazoline ring system, which was converted to the oxazole ring by dehydrogenation (example 3) [5]. Many complex natural products contain oxazole rings, most of which are constructed using this method.
- Example 4: Nicolaou expanded the new uses of this reagent and found that Burgess reagent can be very effective in completing many non-dehydration synthetic tasks when applied to appropriate substrates. For example, with Burgess reagent, sulfonamides are formed from 1,2-diols or epoxy alcohols, α- and β-glycosamines are formed from carbohydrates, and cyclic sulfonamides are formed from 1,2-amino alcohols (example 4) [6]. Subsequently, Hudliky reported that this reagent can also be used with epoxy compounds to obtain aminosulfonic acid lactones, which are then converted into cis- or trans-β-amino alcohols. Besides, this method has a chiral version, and the ee value of the synthesized 8-amino alcohol can reach 84%~98%.
Fig 3. Various synthetic examples with Burgess reagent.
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References
- Li, J.J. Name Reactions. Springer, Cham., Burgess reagent. 2021, pp 64-66.
- Wipf P, et al. Tetrahedron, 1998, 54(25), 6987-6998.
- Rigby J H, et al. Journal of the American Chemical Society, 1997, 119(51), 12655-12656.
- Baran P S, et al. Journal of the American Chemical Society, 2005, 127(44): 15394-15396.
- Tavares F, et al. Journal of the American Chemical Society, 1996, 118(13): 3303-3304.
- Nicolaou K C, et al. Chemistry–A European Journal, 2004, 10(22), 5581-5606.
