TransitionMetalFree C(sp2)—H Phosphorothiolation Cyclization of oHydroxyarylenaminones Access to S3Chromon Phosphorothioat.docx

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1、Synthesis & CatalySiS*W) Check for updatesdoi.org10.1002adsc.202200089Transition-Metal-Free C(sp2) H PhosphorothiolationZCyclizationof O-Hydroxyarylenaminones: Access to S-3-ChromonPhosphorothioatesBiao Zhang,+a Zhonghui Fu,+a Haoqi Yang,a Donghan Liu,a Yulin Sun,aYu Xu,c Fuchao Yu,，* and Sheng-Jiao

2、 Yank*a Faculty of Life Science and Technology, Kunming University of Science and Technology, Kunming, 650500, Peoples Republic of ChinaE-mail: yufuchao05 bKey Laboratory of Medicinal Chemistry for Natural Resources, Ministrj, ofEducation and Yunnan Province, School of Chemical Science and Technolog

3、y, Yunnan University, Kunming 650091, People,s Republic of ChinaE-mail: yansjc School of nursing, Xi,An Innovation College of Yan,An University, Xi,An, 710100, Peoples Republic of ChinaB. Zhang and Z. Fu contributed equally to this work.Manuscript received: January 26, 2022; Revised manuscript recei

4、ved: March 6, 2022 ; Version of record online: March 29, 2022Q Supporting information for this article is available on the WWW under https:/doi.org/10.1 (X)2adsc.2022()0089Abstract: The C(SP?) H phosphorothiolation involving cyclization process through a transitionmetal-free strategy is reported. It

5、 provides an attractive approach for the construction valuable 53-chromon phosphorothioates from o- hydroxyarylenaminones and P(O)SH compounds in the presence of 1.0 equiv. of iodine at 60. This novel protocol shows readily available chemicals, broad substrate scope, and mild reaction conditions.Key

6、words:Phosphorothiolation;o-Hydroxyarylenaminones;S-3-Chromonphosphorothioates; Transition-metal-freePhosphorothoates, which contain the S P(O)(O)2 moiety, have received considerable attention due to their prominent biological properties in agrochemicals and pharmaceuticals.111 In addition, they hav

7、e also functioned as useful building blocks in organic synthesis involving the formation of C S, C C, and C F bonds. Consequently, the development of efficient approaches for constructing phosphorothioates is strongly desired.Among all of the synthetic methods access to phosphorothioates, most of ap

8、plications are implemented through the following six syntheticStrategies (Scheme la): (1) the Michaelis-Arbuzov-type reaction of sulfonyl halides, sulfenyl halides, disulfides or other derivatives with P(O)H compounds;(2) the condensation of thiols with phosphorochloridates or Phosphorobromidates; 1

9、41 (3) the oxidative crossdehydrogenative coupling of thiols with P(O)H compounds; 151 (4) the multicomponent coupling of arylboronic acids, diaryliodonium, or arenediazonium salts with elemental sulfur (Ss) and P(O)H compounds; (5) the phosphorothiolation of alkyl halides, arylboron ic acids, or ar

10、enedi azonium salts with new phosphorothiolation reagents (such as phosphorothioic acids and phosphorothiolate salts);171 (6) the phosphorothiolation of thiols or disulfides with elemental phosphorus.181 Although significant progress has been established in phosphorothiolation field, there are still

11、 encounter challenges in introducing other functionalizations or involving Cyclilation processes along with phosphorothiolation (Scheme lb). Indeed, in terms of multi functionalizations involving phosphorothiolation, there are only two cases of fluoroalkyIphosphorothiolation of alkenes (C C single b

12、onds were formed) described by Zhang et al.191 and one case of aminophosphorothiolalion of alkenes (C=C double bonds were retained) described by Wu et al.1101 However, to the best of our knowledge, there exists no report on phosphorothiolation of alkenes involving Cyclilation processes.Chromones, es

13、pecially 3-functionalized chromones, have recently received considerable attention as they possess many physiological and biological activities.11 (a) General methords for the synthesis of phosphorothoates:OO-CQl MicaelsArtjzovtype reactionCaIR-SY . H-P z,rfc1R-SH . X-PT - r-s-p-OR0R,xOR,S801R-Z or

14、NH4SCNPhosphorothiolation 5aO r-s-por, OR,inorganic sulfur sourceZH. B(OH)2. Br, N2BF4. etc.9 OR1Phosphorotbiolation via new posphxothMaton reagentsQ oriR-S PorR-Z YS-FvOROROR,Z B(OH)2, Br. OH, etc; Y = H, N,Me2. MPhthalimide.R-SHPhosphorylabon from P4OR-S-RTsr SRC c f P4R-SS-RX = , Br9 2l S-Hphoeph

15、orytetion r,oR-SH . H-Pu- R-S-Ponahzation (challenge)Phosphorothiolation /difunctionalizationthree examples1aOO HS-k0t OEt2aq了费EntrySolventI (eq.)T (eC)t(h)Yield (%)1MeCNh(1.0)604912MeCNI2O5(l.O)608473MeCNNIS (1.0)608654MeCNNaI(LO)608n.d.c)5MeCNTBAI(LO)608n.d.c6MeCNNH4I(LO)608trace7DCMI2(LO)608238THFh(1.0)608