Cascade Cross-Coupling/[3,3]-Sulfonium Rearrangement of Alkynyl Sulfoxides and Ynamides/Ynol Ethers to Construct Tetrasubstituted Furans

doi:10.6023/cjoc202401016

Abstract

A transition-metal-free strategy for the synthesis of tetrasubstituted furans is reported. Promoted by boron trifluoride diethyl etherate, the reaction of alkynyl sulfoxides with ynamides/ynol ethers proceeded via a cascade process including cross-coupling of the two reactants, [3,3]-sulfonium rearrangement, and 5-exo-dig heterocyclization, leading to tetrasubstituted furan products. The resultant α-alkylthio groups can be used for further functionalization, such as to introduce other alkyl/aryl groups.

Key words: heterocyclization, [3,3]-rearrangement, sulfonium ion, tandem reaction, tetrasubstituted furan

Cite this article

Shuyu Meng, Wentao Guo, Quanrui Wang. Cascade Cross-Coupling/[3,3]-Sulfonium Rearrangement of Alkynyl Sulfoxides and Ynamides/Ynol Ethers to Construct Tetrasubstituted Furans[J]. Chinese Journal of Organic Chemistry, 2024, 44(7): 2274-2285.

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Fig. & Tab. 8

Scheme 1. Typical examples of polysubstituted furan synthesis based on rearrangement strategy

Scheme 2. Applications of [3,3]-sulfonium rearrangement strategy reported by Maulide group[8]

Scheme 3. Cascade cross-coupling/[3,3]-sulfonium rearrangement strategy for accessing tetrasubstituted furans and the putative mechanism

Entry	Variation from standard conditions	Conv. 4a^b/%
1	None	58 (51)^c
2	With 2.0 equiv. of ynamide 1a	58
3	With 20 mol% BF₃•OEt₂	31
4	With 50 mol% BF₃•OEt₂	50
5	r.t. o/n instead of 70 ℃	51 (43)^c
6	1.0 equiv. of TfOH/AuCl₃/AgSbF₆	47/18/13
7	BF₃•OEt₂ added via a syringe pump	25

Table 1. Optimization of the reaction condition with ynamide 1a and alkynyl sulfoxide 3aa

Scheme 4. Scope study of the reaction with ynamides/ynamines and the crystal structures of furans 4f and 4j

Entry	Variation from standard conditions	Conv. 5a^b/%
1	None	49 (44)^c
2	With 1.5 equiv. of ynol ether 2a	30 (23)^c
3	With 3.0 equiv. of ynol ether 2a	45
4	With 20 mol% BF₃•OEt₂	15
5	r.t. o/n instead of 70 ℃	39
6	1.0 equiv. of TfOH	38
7	BF₃•OEt₂ added via a syringe pump	33

Table 2. Optimization of the reaction with ynol ether 2a and alkynyl sulfoxide 3aa

Scheme 5. Scope of the reaction with ynol ethers

Scheme 6. Post-modification of tetrasubstituted α-aminofurans 4

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