synthesis of chiral sulfonyl lactones via copper‐catalyzed

6
Synthesis of Chiral Sulfonyl Lactones via Copper-Catalyzed Asymmetric Radical Reaction of DABCO·(SO 2 ) Yang Wang, a Lingling Deng, a Jie Zhou, b Xiaochen Wang, a Haibo Mei, a Jianlin Han, a, * and Yi Pan a a School of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, Nanjing University, 210093, People’s Republic of China phone number: 86-25-83686133 E-mail: [email protected] b Shenzhen Research Institute of Nanjing University, Shenzhen, 518057, People)s Republic of China Received: December 3, 2017; Revised: December 14, 2017; Published online: January 15, 2018 Supporting information for this article is available on the WWW under https://doi.org/10.1002/adsc.201701532 Abstract: In the present work, an asymmetric copper-catalyzed radical multi-component cascade reaction of an unsaturated carboxylic acid, aryldia- zonium tetrafluoroborate, and DABCO·(SO 2 ) 2 (DABSO) has been developed for the enantioselec- tive synthesis of sulfonyl lactones. In this reaction, this SO 2 surrogate, DABSO was applied for the first time in the construction of chiral compounds. This multiple-step asymmetric radical reaction was carried out under mild conditions and tolerated a wide range of substrates, resulting in the corre- sponding sulfonyl lactones with up to 95% chemical yields and 88% ee. The current reaction enriches the research contents of DABSO, and provides a new and efficient strategy to chiral functionalized lactones bearing quarternary stereogenic center. Keywords: asymmetric catalysis; radical reaction; Cu-catalysis; DABSO; lactones Sulfones represent an important type of organic compounds and widely exist in many natural products and pharmaceutical molecules. [1] Also, they are useful organic intermediates, and such sulfonyl structural units have been widely applied in many organic transformations. [2] Traditional methods for the syn- thesis of sulfones usually focus on oxidation of sulfides [3] or sulfonylation of C(sp 2 ) À H and C(sp 3 ) À H bonds. [4] Recently, many elegant methods using of DABCO·(SO 2 ) 2 (DABSO) as an SO 2 surrogate for the preparation of sulfonyl compounds have been devel- oped independently by the Willis, [5] Wu [6] and other groups, [7] which allows the direct introduction of a sulfonyl group through SO 2 insertion under simple conditions. Although great achievements have been made on this SO 2 surrogate (Scheme 1a), [5–8] this useful reagent has never been explored in enantiose- lective synthesis. Chiral structures play an important role in natural products, pharmaceuticals, and other bioactive com- pounds. [9,10] In the past decades enantioselective ionic reactions have been well developed. However, asym- metric radical reactions remain less reported, mainly because radicals are considered to be disadvantaged in the formation of chiral centers because they are highly reactive and short-lived. [11] In recent years, enantiose- lective radical reactions attracted the attention of many research groups. [12] For example, the Liu group has developed a series of catalytic asymmetric difunc- tionalization of alkenes via a radical process. [13] On the other hand, the Liu group has also developed several novel reactions on direct asymmetric radical difunc- tionalization of unactivated alkenes with copper salts and chiral phosphoric acid as combined catalyst. [14] Recently, Buchwald [15] and co-workers developed two examples of asymmetric Cu-catalyzed radical oxy- trifluoromethylation of alkenes with Togni’s reagent or other coupling partners. Considering that DABSO has never been applied in asymmetric reactions and Scheme 1. Radical coupling reaction of DABSO. COMMUNICATIONS DOI: 10.1002/adsc.201701532 Adv. Synth. Catal. 2018, 360, 1060 – 1065 1060 # 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Upload: others

Post on 31-Jan-2022

12 views

Category:

Documents


0 download

TRANSCRIPT

Page 1: Synthesis of Chiral Sulfonyl Lactones via Copper‐Catalyzed

123456789

101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657

Synthesis of Chiral Sulfonyl Lactones via Copper-CatalyzedAsymmetric Radical Reaction of DABCO·(SO2)

Yang Wang,a Lingling Deng,a Jie Zhou,b Xiaochen Wang,a Haibo Mei,a

Jianlin Han,a,* and Yi Pana

a School of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Jiangsu KeyLaboratory of Advanced Organic Materials, Nanjing University, 210093, People’s Republic of Chinaphone number: 86-25-83686133E-mail: [email protected]

b Shenzhen Research Institute of Nanjing University, Shenzhen, 518057, People�s Republic of China

Received: December 3, 2017; Revised: December 14, 2017; Published online: January 15, 2018

Supporting information for this article is available on the WWW under https://doi.org/10.1002/adsc.201701532

Abstract: In the present work, an asymmetriccopper-catalyzed radical multi-component cascadereaction of an unsaturated carboxylic acid, aryldia-zonium tetrafluoroborate, and DABCO·(SO2)2

(DABSO) has been developed for the enantioselec-tive synthesis of sulfonyl lactones. In this reaction,this SO2 surrogate, DABSO was applied for thefirst time in the construction of chiral compounds.This multiple-step asymmetric radical reaction wascarried out under mild conditions and tolerated awide range of substrates, resulting in the corre-sponding sulfonyl lactones with up to 95% chemicalyields and 88% ee. The current reaction enrichesthe research contents of DABSO, and provides anew and efficient strategy to chiral functionalizedlactones bearing quarternary stereogenic center.

Keywords: asymmetric catalysis; radical reaction;Cu-catalysis; DABSO; lactones

Sulfones represent an important type of organiccompounds and widely exist in many natural productsand pharmaceutical molecules.[1] Also, they are usefulorganic intermediates, and such sulfonyl structuralunits have been widely applied in many organictransformations.[2] Traditional methods for the syn-thesis of sulfones usually focus on oxidation ofsulfides[3] or sulfonylation of C(sp2)�H and C(sp3)�Hbonds.[4] Recently, many elegant methods using ofDABCO·(SO2)2 (DABSO) as an SO2 surrogate for thepreparation of sulfonyl compounds have been devel-oped independently by the Willis,[5] Wu[6] and othergroups,[7] which allows the direct introduction of asulfonyl group through SO2 insertion under simpleconditions. Although great achievements have been

made on this SO2 surrogate (Scheme 1a),[5–8] thisuseful reagent has never been explored in enantiose-lective synthesis.

Chiral structures play an important role in naturalproducts, pharmaceuticals, and other bioactive com-pounds.[9,10] In the past decades enantioselective ionicreactions have been well developed. However, asym-metric radical reactions remain less reported, mainlybecause radicals are considered to be disadvantaged inthe formation of chiral centers because they are highlyreactive and short-lived.[11] In recent years, enantiose-lective radical reactions attracted the attention ofmany research groups.[12] For example, the Liu grouphas developed a series of catalytic asymmetric difunc-tionalization of alkenes via a radical process.[13] On theother hand, the Liu group has also developed severalnovel reactions on direct asymmetric radical difunc-tionalization of unactivated alkenes with copper saltsand chiral phosphoric acid as combined catalyst.[14]

Recently, Buchwald[15] and co-workers developed twoexamples of asymmetric Cu-catalyzed radical oxy-trifluoromethylation of alkenes with Togni’s reagentor other coupling partners. Considering that DABSOhas never been applied in asymmetric reactions and

Scheme 1. Radical coupling reaction of DABSO.

COMMUNICATIONS DOI: 10.1002/adsc.201701532

Adv. Synth. Catal. 2018, 360, 1060 – 1065 1060 � 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Page 2: Synthesis of Chiral Sulfonyl Lactones via Copper‐Catalyzed

123456789

101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657

inspired by the above asymmetric radical works,[13–16]

we herein report the first example of an asymmetriccopper-catalyzed radical multi-component reaction ofunsaturated carboxylic acids, aryldiazonium tetrafluor-oborates,[17] and DABSO (Scheme 1b). This Cu-cata-lyzed asymmetric cyclization reaction is conducted atroom temperature, and proceeds through a four-stepradical pathway, affording the chiral sulfonyl lactoneswith up to 95% yields and 88% ee. Furthermore, thisradical multi-component reaction provides a newmethod for the synthesis of chiral sulfonyl lactones. Itshould be mentioned that the Wu group recentlyreported a related visible light-promoted radicalcyclization reaction of 2-vinylbenzoic acids, aryldiazo-niumtetra fluoroborates and sulfur dioxide surrogateof DABCO·(SO2)2 for the preparation of sulfonatedisobenzofuran-1(3H)-ones.[18]

To test the possibility of this strategy, we chose 4-phenylpent-4-enoic acid 1 a, 4-methylbenzenediazo-nium tetrafluoroborate 2a and DABSO as modelsubstrates for the initial study. The reaction wascarried out in the presence of 2,6-di-tert-butylpyridinewith Cu(OAc) as catalyst, bis((S)-4-(tert-butyl)-4,5-dihydrooxazol-2-yl)methane (L1) as chiral ligandunder argon atmosphere at room temperature. Thereaction did happen, and the corresponding sulfonyllactone 3 aa was obtained in 46% yield and 36% eeafter 12 h (entry 1, Table 1). Other catalysts, such asCuBr and Cu(OTf)2, also catalyzed this transforma-tion resulting in similar yields and enantioselectivities(entries 2 and 4). An obvious improvement on yieldwas found when Cu(OAc)2 was used (60% yield,entry 3). [Cu(MeCN)4]PF6 was demonstrated to be thebest one, and furnished the product 3 aa in 80% yieldand 56% ee (entry 5). The reaction did not take placewith other metal catalysts, such as NiCl2 and NiI2

(entries 6 and 7). Then, the chiral ligand was scannedfor this reaction (for details on the optimization ofchiral ligands, see Supporting Information). There wasan obviously reduction on ee value when the chiralligand was replaced by bis((S)-4-isopropyl-4,5-dihy-drooxazol-2-yl)methane (L2) (entry 8, 71% yield and21% ee). The similar result was observed with bis((S)-4-phenyl-4,5-dihydrooxazol-2-yl)methane (L3) as li-gand (60% yield and 26% ee, entry 9). Other bisox-azoline ligands also have been tried, however, noimprovement on the enantioselectivity was found(entries 10 and 11). The solvent also showed obviouseffect on the reaction outcome. Reaction in CH2Br2

provided the same level of yield and ee (entry 14, 75%yield, 52% ee). Other solvents, such as DCE,CHCl2CH2Cl and 1,4-dioxane, gave obviously loweryields and enantioselectivities (entries 12, 13 and 15).Finally, different bases were tested as additives for thisreaction. When DABCO was added instead of 2,6-di-tert-butylpyridinein (DTBP), similar ee was obtained,but with dramatically decreased yield (entry 16, 56%

ee and 34% yield). Inorganic base, like Ag2CO3, couldpromote the reaction to give the correspondingproduct, but still no improvement on yield andenantioselectivity was obtained (entry 18, 65% yieldand 54% ee).

With the optimal conditions in hand, we theninvestigated the substrate scope of this Cu-catalyzedasymmetric reaction by using various unsaturatedcarboxylic acids, and the results are shown inScheme 2.

First, several 4-arylpent-4-enoic acid substrateswere tested for the construction of five-member ringlactones (3 aa–3 ha). The p-tolyl substituted unsatu-rated carboxylic acids provided the correspondingproduct 3 ba in good yield (81%) and ee (64%). Thesubstrate with strong electron-donating group substi-tuted phenyl, 4-methoxyphenyl unsaturated carboxylicacids 1 c, afforded the product 3ca in excellent yield(95%), but with low ee (22%). In contrast, when thesubstrate with para-phenyl substituted phenyl, thereaction showed an opposite outcome, and the desiredproduct 3da was obtained in excellent ee (88%) butpoor yield (25%). The substrates with electron-with-drawing groups also worked well in this reaction(3 ea–3 ga). Even the 4-fluorophenyl substituted one1 g was tolerated, affording 3 ga in 60% yield and 44%ee. To investigate the steric effect of the currentsystem, one substrate with two phenyl groups on thea-position, 4-methyl-2,2-diphenylpent-4-enoic acid 1h,was tried. Unfortunately, the corresponding product3 ha was obtained with only 6% ee and 56% chemicalyield. Interestingly, 5-phenylhex-5-enoic acid was alsoa suitable substrate, affording the six-membered

Scheme 2. Substrate scope of unsaturated carboxylic acids.

COMMUNICATIONS asc.wiley-vch.de

Adv. Synth. Catal. 2018, 360, 1060 – 1065 1061 � 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Page 3: Synthesis of Chiral Sulfonyl Lactones via Copper‐Catalyzed

123456789

101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657

lactone derivative 3 ia in 60% yield and 12% ee.Finally, several ortho-vinyl benzoic acid derivatives

were tried in this reaction due to the importance ofisobenzofuran-1-ones motif in bioorganic chemistry.The substrates without a substituted group or with anelectron-donating group on the aromatic ring, reactedwell with DABSO and 4-methylbenzenediazoniumtetrafluoroborate to give the desired product withmoderate yields (3 ja–3 ka). However, in the case ofthe substrate bearing electron-withdrawing groupsubstituted phenyl, the reaction gave very poor yield(10%, 3 la).

Next, we concentrated on the study of substrategenerality of aryl diazonium salts, and the results areshown in Scheme 3.

Benzenediazonium salt 2 b was suitable substratefor this reaction, which gave the lactone 3 ab inmoderate yield (54%) and ee (54%). On the otherhand, varieties of functional groups in para position ofphenyl ring, such as t-butyl (3 ac), methoxyl (3 ad),fluoro (3 ae), nitro (3af), chloro (3 ag) and trifluor-omethyl (3ah), could be well tolerated in the reaction,resulting in the desired product with up to 71% yieldand 74% ee. Notably, even the substrates containingstrong electron-donating or electron-withdrawinggroup could work well in this system, affording thedesired product in the same level of yield and ee (71%yield and 56% ee for 3 ad, 64% yield and 54% ee for3 ae, 50% yield and 74% ee for 3 ah respectively). Thesubstrate bearing ortho-substituted group has alsobeen tested in the reaction. However, both the yieldand ee were poor because of the steric hindrance(30% yield and 42% ee for 3 ai, 55% yield and 44% eefor 3 aj). It should be mentioned that the reaction ofdisubstituted benzenediazonium salt also proceeded

Table 1. Optimization of the reaction conditions.[a]

Entry Catalyst L Solvent Yield(%)[b]

Ee(%)[c]

1 Cu(OAc) L1 DCM 46 362 CuBr L1 DCM 39 353 Cu(OAc)2 L1 DCM 60 404 Cu(OTf)2 L1 DCM 41 405 Cu(MeCN)4

PF6

L1 DCM 80 56

6 NiCl2 L1 DCM trace -7 NiI2 L1 DCM trace -8 Cu(MeCN)4

PF6

L2 DCM 71 21

9 Cu(MeCN)4

PF6

L3 DCM 60 26

10 Cu(MeCN)4

PF6

L4 DCM 76 30

11 Cu(MeCN)4

PF6

L5 DCM 61 26

12 Cu(MeCN)4

PF6

L1 DCE 58 53

13 Cu(MeCN)4

PF6

L1 1,4-dioxane 50 47

14 Cu(MeCN)4

PF6

L1 CH2Br2 75 52

15 Cu(MeCN)4

PF6

L1 CHCl2CH2Cl 64 54

16[d] Cu(MeCN)4

PF6

L1 DCM 34 56

17[e] Cu(MeCN)4

PF6

L1 DCM 52 52

18[f] Cu(MeCN)4

PF6

L1 DCM 65 54

[a] Reaction conditions: 1 a (0.2 mmol), 2 a (0.4 mmol,2.0 equiv.), DABSO (0.2 mmol, 1.0 equiv.), additive(0.4 mmol, 2.0 equiv.), catalyst (0.02 mmol, 10 mol%),ligand (0.024, 12 mol%), 2,6-di-tert-butylpyridine(0.4 mmol, 2.0 equiv.), under argon atmosphere for 12 h.

[b] Isolated yields.[c] Enantiomeric excess (ee) was determined by HPLC on a

chiral stationary phase.[d] DABCO as additive.[e] DBU as additive.[f] Ag2CO3 as additive.

Scheme 3. Substrate scope of aryl diazonium salts. (Thecorrected Scheme 3 was provided)

COMMUNICATIONS asc.wiley-vch.de

Adv. Synth. Catal. 2018, 360, 1060 – 1065 1062 � 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Page 4: Synthesis of Chiral Sulfonyl Lactones via Copper‐Catalyzed

123456789

101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657

smoothly, affording the corresponding product in goodyield and enantioselectivity (3 ak, 88% yield and 78%ee). Finally, a benzyl diazonium salt was examined inthis reaction, which did not work at all with most ofthe starting materials remained. The absolute config-uration of these sulfonyl lactones has been determinedby the x-ray analysis of 3 ac, which discloses its (S)absolute configuration (see SI file).[19] Accordingly, allthe other products 3 were assigned (S) stereochemis-try.

To get insight into the mechanism of this Cu-catalyzed asymmetric reaction, two control experi-ments were carried out (Scheme 4). First, a radicaltrapping experiment was carried out under standardconditions with the addition of TEMPO [(2,2,6,6-tetramethylpiperidin-1-yl)oxyl] (Scheme 4a). The re-action was totally suppressed and only a trace amountof the desired product 3 aa was found. To verify radicalprocess, another radical scavenger 1,1-diphenylalkenewas added to the reaction under standard reactionconditions (Scheme 1b). The similar result was foundand almost no 3 aa was obtained. After carefulisolation of the reaction mixture, 1,1-diphenylalkene-toluene radical adduct 4 was obtained in 56% isolatedyield.

Based on the above results and previous re-ports,[5�7,15] a possible mechanism is illustrated inScheme 5. Initially, phenyldiazonium tetrafluorobo-rate 2 b is reduced by Cu(I) via single-electron-transferto generate phenyl radical and Cu(II) complex A viarelease of nitrogen.[17c] This phenyl radical is trappedby DABCO·(SO2)2 and generates the benzene sulfonylradical. At the same time, unsaturated carboxylic acid1 a reacts with A in the presence of 2,6-di-tert-butylpyridine in to give the Cu(II)-unsaturated car-boxylic acids complex B. Then, intermediate B coupleswith benzene sulfonyl radical leading to the radicalintermediate C.[15b] Although the radical nature of theunobservable transient intermediate is an disadvant-age, the possible interaction between Cu(II) andcarbon radical may be helpful for the enantioselectivecontrol of this reaction. Subsequently, a single electron

oxidation process of intermediate C happens, afford-ing the Cu(III) complex as well as the formation ofchiral center. Finally, reductive elimination of thisCu(III) intermediate D to give the final chiral product3 ab and regenerate the Cu(I) for the next catalyticcycle. It should be mentioned that aryl sulfonyl radicalmay also generate from the reaction between aryldia-zonium tetrafluoroborate and DABCO·(SO2)2.

[20]

In conclusion, we have developed a novel methodto prepare sulfonyl lactones bearing quanternarystereogenic center via copper-catalyzed asymmetricradical cascade multi-component reaction of unsatu-rated carboxylic acids. In this reaction, DABSO wasused as sulfonyl precursor and aryldiazonium tetra-fluoroborate was used as aryl radical, to give thecorresponding product with good chemical yields andenantioselectivities. In particular, this SO2 surrogatewas used for first time in synthesis of functionalizedchiral compounds, which enriches the research con-tents of reactions on DABSO and asymmetric radicalreactions.

Experimental SectionGeneral Procedures for Copper-CatalyzedAsymmetric Radical Reaction of UnsaturatedCarboxylic acids, Aryldiazonium Tetrafluoroborates,and DABSO.

The bisoxazoline ligand L1 (6.4 mg, 0.024 mmol) andCu(MeCN)4PF6 (7.5 mg, 0.020 mmol) were dissolved in 2 mLof anhydrous DCM under argon at room temperature andstirred for 2 h. Then the solution was inject into a bottlewhich was filled with argon, unsaturated carboxylic acids 1(0.2 mmol), aryldiazonium salts 2 (0.4 mmol), DABSO(0.2 mmol) and 2,6-di-tert-butylpyridine (0.4 mmol). Themixture was stirred for another 12 h at room temperature.

Scheme 4. Radical trapping experiment.

Scheme 5. Proposed mechanism.

COMMUNICATIONS asc.wiley-vch.de

Adv. Synth. Catal. 2018, 360, 1060 – 1065 1063 � 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Page 5: Synthesis of Chiral Sulfonyl Lactones via Copper‐Catalyzed

123456789

101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657

The solvent was removed under reduced pressure, and theresidue was purified by silica gel column chromatography(PE:EA=10:1) to afford products 3.

AcknowledgementsWe gratefully acknowledge the financial support from theNational Natural Science Foundation of China(No. 21772085). The support from Collaborative InnovationCenter of Solid-State Lighting and Energy-Saving Electronics,Shenzhen Virtual University Park and Changzhou Jin-Feng-Huang program (for Han) are also acknowledged.

References

[1] a) T. D. Penning, J. J. Talley, S. R. Bertenshaw, J. S.Carter, P. W. Collins, S. Docter, M. J. Graneto, L. F. Lee,J. W. Malecha, J. M. Miyashiro, R. S. Rogers, D. J.Rogier, S. S. Yu, G. D. Anderson, E. G. Burton, J. N.Cogburn, S. A. Gregory, C. M. Koboldt, W. E. Perkins,K. Seibert, A. W. Veenhuizen, Y. Y. Zhang, P. C.Isakson, J. Med. Chem. 1997, 40, 1347–1365; b) P.Zoumpoulakis, C. Camoutsis, G. Pairas, M. Sokovic, J.Glamoclija, C. Potamitis, A. Pitsas, Bioorg. Med. Chem.2012, 20, 1569–1583.

[2] a) R. Tanikaga, K. Hosoya, A. Kaji, J. Chem. Soc.Perkin 1 1987, 0, 1799–1803; b) A. P. Kozikowski, B. B.Mugrage, C. S. Li, L. Felder, Tetrahedron Lett. 1986, 27,4817–4820; c) S. Robin, F. Huet, A. Fauve, H. Vescham-bre, Tetrahedron Asymmetry 1993, 4, 239–246.

[3] a) C. Dai, J. Zhang, C. Huang, Z. Lei, Chem. Rev. 2017,117, 6929–6983; b) J. Aziz, S. Messaoudi, M. Alami, A.Hamze, Org. Biomol. Chem. 2014, 12, 9743–9759;c) K. Y. Liu, H. Qu, X. Y. Shi, X. F. Dong, W. J. Ma, J. F.Wei, Chinese J. Org. Chem. 2014, 34, 681–692.

[4] a) S. Shaaban, S. Liang, N. W. Liu, G. Manolikakes, Org.Biomol. Chem. 2017, 15, 1947–1955; b) Y. Fang, Z. Luo,X. Xu, RSC Adv. 2016, 6, 59661–59676.

[5] a) E. F. Flegeau, J. M. Harrison, M. C. Willis, Synlett2016, 27, 101–105; b) Y. Chen, M. C. Willis, Chem. Sci.2017, 8, 3249–3253; c) A. T. Davies, J. M. Curto, S. W.Bagley, M. C. Willis, Chem. Sci. 2017, 8, 1233–1237;d) A. S. Deeming, C. J. Russell, M. C. Willis, Angew.Chem. Int. Ed. 2016, 55, 747–750; e) C. S. Richards-Taylor, D. C. Blakemore, M. C. Willis, Chem. Sci. 2013,5, 222–228; f) H. Woolven, C. Gonz�lez-Rodr�guez, I.Marco, A. L. Thompson, M. C. Willis, Org. Lett. 2011,13, 4876–4878; g) B. Nguyen, E. J. Emmett, M. C. Willis,J. Am. Chem. Soc. 2010, 132, 16372–16373; h) A. S.Deeming, C. J. Russell, M. C. Willis, Angew. Chem. Int.Ed. 2015, 54, 1168–1171.

[6] a) Y. Xiang, Y. Li, Y. Kuang, J. Wu, Chem. Eur. J. 2017,23, 1032–1035; b) T. Liu, D. Zheng, Y. Ding, X. Fan, J.Wu, Chem. Asian J. 2017, 12, 465–469; c) J. Yu, R. Mao,Q. Wang, J. Wu, Org. Chem. Front. 2017, 4, 617–621;d) T. Liu, D. Zheng, J. Wu, Org. Chem. Front. 2017, 4,1079–1083; e) Y. Li, Y. Xiang, Z. Li, J. Wu, Org. Chem.Front. 2016, 3, 1493–1497; f) Y. Li, D. Zheng, Z. Li, J.Wu, Org Chem Front 2016, 3, 574–578; g) D. Zheng, Y.

Li, Y. An, J. Wu, Chem. Commun. 2014, 50, 8886–8888;h) Y. An, D. Zheng, J. Wu, Chem Commun 2014, 50,11746–11748; i) D. Zheng, Y. An, Z. Li, J. Wu, Angew.Chem. Int. Ed. 2014, 53, 2451–2454.

[7] a) C. C. Chen, J. Waser, Org. Lett. 2015, 17, 736–739;b) B. Du, Y. Wang, W. Sha, P. Qian, H. Mei, J. Han, Y.Pan, Asian J. Org. Chem. 2017, 2, 153–156; c) B. N.Rocke, K. B. Bahnck, M. Herr, S. Lavergne, V. Mascitti,C. Perreault, J. Polivkova, A. Shavnya, Org. Lett. 2014,16, 154–157; d) A. L. Tribby, I. Rodr�guez, S. Shariffu-din, N. D. Ball, J. Org. Chem. 2017, 82, 2294–2299;e) A. S. Tsai, J. M. Curto, B. N. Rocke, A. R. Dechert-Schmitt, G. K. Ingle, V. Mascitti, Org. Lett. 2016, 18,508–511; f) N. von Wolff, J. Char, X. Frogneux, T.Cantat, Angew. Chem. Int. Ed. 2017, 56, 5616–5619;g) C. Waldmann, O. Schober, G. Haufe, K. Kopka, Org.Lett. 2013, 15, 2954–2957; h) X. Wang, L. Xue, Z. Wang,Org. Lett. 2014, 16, 4056–4058.

[8] a) M. W. Johnson, S. W. Bagley, N. P. Mankad, R. G.Bergman, V. Mascitti, F. D. Toste, Angew. Chem. Int.Ed. 2014, 53, 4404–4407; b) A. Shavnya, S. B. Coffey,A. C. Smith, V. Mascitti, Org. Lett. 2013, 15, 6226–6229;c) A. Shavnya, K. D. Hesp, V. Mascitti, A. C. Smith,Angew. Chem. Int. Ed. 2015, 54, 13571–13575; d) N.Umierski, G. Manolikakes, Org. Lett. 2013, 15, 4972–4975; e) Y. Wang, B. Du, W. Sha, H. Mei, J. Han, Y. Pan,Org. Chem. Front. 2017, 4, 1313–1317; f) H. Zhu, Y.Shen, Q. Deng, J. Chen, T. Tu, ACS Catal. 2017, 7,4655–4659;

[9] a) A. Lorente, J. Lamariano-Merketegi, F. Albericio, M.�lvarez, Chem. Rev. 2013, 113, 4567–4610; b) E. J.Kang, E. Lee, Chem. Rev. 2005, 105, 4348–4378.

[10] M. M. Faul, B. E. Huff, Chem. Rev. 2000, 100, 2407–2474.

[11] a) M. P. Sibi, S. Manyem, J. Zimmerman, Chem. Rev.2003, 103, 3263–3296; b) M. P. Sibi, N. A. Porter, Acc.Chem. Res. 1999, 32, 163–171.

[12] a) K. Ding, Prog. Chem. 2017, 29, 13–14; b) D. Wang, L.Zhang, S. Luo, Acta Chim. Sinica 2017, 75, 22–33; c) M.Yan, J. C. Lo, J. T. Edwards, P. S. Baran, J. Am. Chem.Soc. 2016, 138, 12692–12714; d) K. Nakajima, Y.Miyake, Y. Nishibayashi, Acc. Chem. Res. 2016, 49,1946–1956.

[13] a) D. Wang, L. Wu, F. Wang, X. Wan, P. Chen, Z. Lin,G. Liu, J. Am. Chem. Soc. 2017, 139, 6811–6814; b) L.Wu, F. Wang, X. Wan, D. Wang, P. Chen, G. Liu, J. Am.Chem. Soc. 2017, 139, 2904–2907; c) D. Wang, F. Wang,P. Chen, Z. Lin, G. Liu, Angew. Chem. Int. Ed. 2017, 56,2054–2058; d) F. Wang, D. Wang, X. Wan, L. Wu, P.Chen, G. Liu, J. Am. Chem. Soc. 2016, 138, 15547–15550; e) W. Zhang, F. Wang, S. D. McCann, D. Wang, P.Chen, S. S. Stahl, G. Liu, Science 2016, 353, 1014–1018;f) W. Zhang, P. Chen, G. Liu, Angew. Chem. Int. Ed.2017, 56, 5336–5340.

[14] a) Y. F. Cheng, X. Y. Dong, Q. S. Gu, Z. L. Yu, X. Y.Liu, Angew. Chem. Int. Ed. 2017, 56, 8883–8886; b) J. S.Lin, X. Y. Dong, T. T. Li, N. C. Jiang, B. Tan, X. Y. Liu,J. Am. Chem. Soc. 2016, 138, 9357–9360; c) J. S. Lin,F. L. Wang, X. Y. Dong, W. W. He, Y. Yuan, S. Chen,X. Y. Liu, Nat. Commun. 2017, 8, 14841; d) L. Li, Z. L.Li, F. L. Wang, Z. Guo, Y. F. Cheng, N. Wang, X. W.

COMMUNICATIONS asc.wiley-vch.de

Adv. Synth. Catal. 2018, 360, 1060 – 1065 1064 � 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Page 6: Synthesis of Chiral Sulfonyl Lactones via Copper‐Catalyzed

123456789

101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657

Dong, C. Fang, J. Liu, C. Hou, B. Tan, X. Y. Liu, Nat.Commun. 2016, 7, 13852; e) Z. L. Li, X. H. Li, N. Wang,N. Y. Yang, X. Y. Liu, Angew. Chem. Int. Ed. 2016, 55,15100–15104.

[15] a) R. Zhu, S. L. Buchwald, Angew. Chem. Int. Ed. 2013,52, 12655–12658; b) R. Zhu, S. L. Buchwald, J. Am.Chem. Soc. 2015, 137, 8069–8077.

[16] a) W. Sha, Y. Zhu, H. Mei, J. Han, V. A. Soloshonok, Y.Pan, ChemistrySelect 2017, 2, 1129–1132; b) Z. G. Brill,H. K. Grover, T. J. Maimone, Science 2016, 352, 1078–1082; c) X. Shen, K. Harms, M. Marsch, E. Meggers,Chem. Eur. J. 2016, 22, 9102–9105.

[17] a) K. Shin, S. W. Park, S. Chang, J. Am. Chem. Soc.2015, 137, 8584–8592; b) S. J. Kwon, D. Y. Kim, Org.Lett. 2016, 18, 4562–4565; c) Y. Xiang, Y. Kuang, J. Wu,Chem. Eur. J. 2017, 23, 6996–6999; d) Y. Liu, R. J. Song,J. H. Li, Chem. Commun. 2017, 53, 8600–8603.

[18] J. Zhang, K. Zhou, J. Wu, Org. Chem. Front. 2018, DOI:10.1039/C7QO00987A.

[19] CCDC-1579954 contains the supplementary crystallo-graphic data for 3 ac. These data can be obtained free ofchargefrom The Cambridge Crystallographic DataCentre via www.ccdc.cam.ac.uk/data_request/cif.

[20] a) D. Zheng, J. Yu, J. Wu, Angew. Chem. Int. Ed. 2016,55, 11925–11929; b) T. Liu, D. Zheng, Z. Li, J. Wu, Adv.Synth. Catal. 2017, 359, 2653–2659; c) X. Wang, T. Liu,D. Zheng, Q. Zhong, J. Wu, Org. Chem. Front. 2017, 4,2455–2458; d) Y. An, J. Wu, Org. Lett. 2017, 19, 6028–6031; e) H. Wang, S. Sun, J. Cheng, Org. Lett. 2017, 19,5844–5847; f) J. Zhang, Y. An, J. Wu, Chem. Eur. J.2017, 23, 9477–9480; g) T. Liu, W. Zhou, J. Wu, Org.Lett. 2017, 10.1021/acs.orglett.7b03365; h) H. Xia, Y.An, X. Zeng, J. Wu, Chem. Commun. 2017, 53, 12548–12551.

COMMUNICATIONS asc.wiley-vch.de

Adv. Synth. Catal. 2018, 360, 1060 – 1065 1065 � 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim