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. 2020 Jan 31;5(5):2440-2457.
doi: 10.1021/acsomega.9b03989. eCollection 2020 Feb 11.

Exploring Possible Surrogates for Kobayashi's Aryne Precursors

Ana Carolina A Muraca  1 , Cristiano Raminelli  1
Affiliations

Exploring Possible Surrogates for Kobayashi's Aryne Precursors

Ana Carolina A Muraca et al. ACS Omega. .

Abstract

A class of aryne precursors, that is, 2-(trimethylsilyl)aryl 4-chlorobenzenesulfonates, has been developed through well-established synthetic routes, which allow the formation of arynes under relatively mild conditions. All the aryne precursors were obtained from phenols and 4-chlorobenzenesulfonyl chloride, an inexpensive and easy-to-handle reagent with relatively low toxicity, and subjected to nucleophilic addition reactions, providing addition products in yields of 24 to 92%, and to cycloaddition reactions, affording cycloadducts in yields up to 80%. This work provides interesting insights into the mechanisms of aryne generation. In addition, 2-(trimethylsilyl)phenyl 4-chlorobenzenesulfonate was successfully employed in the total synthesis of (±)-aporphine.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Previously Reported Alternatives to Silylaryl Triflates and the Novel Benzyne Precursor Introduced by This Work
Scheme 2
Scheme 2. Synthesis of 2-(Trimethylsilyl)phenyl Benzenesulfonates 7a and 10 and 2-(Trimethylsilyl)phenyl Sulfamate (12)
Scheme 3
Scheme 3. Proposed Mechanisms for the Benzyne Generation Using Compound 7a
Scheme 4
Scheme 4. Preparation of 2-(Trimethylsilyl)aryl 4-Chlorobenzenesulfonates 7b–7e
Scheme 5
Scheme 5. Proposed Mechanism for the Formation of 4-Chlorobenzenesulfonates 19a–19c
Scheme 6
Scheme 6. Preparation of Alkyl Azides 25a–25d and Aryl Azides 26a–26d
Scheme 7
Scheme 7. Total Synthesis of Alkaloid (±)-Aporphine (34)
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