[논문]γ -Selective C(sp 3 )–H amination via controlled migratory hydroamination

Lee, Changseok; Seo, Huiyeong; Jeon, Jinwon; Hong, Sungwoo

doi:10.1038/s41467-021-25696-z

[해외논문] γ -Selective C(sp 3 )–H amination via controlled migratory hydroamination 원문보기

Nature communications, v.12 no.1, 2021년, pp.5657 -

Lee, Changseok (Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, 34141 Korea) , Seo, Huiyeong (Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, 34141 Korea) , Jeon, Jinwon (Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, 34141 Korea) , Hong, Sungwoo (Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), Daejeon, 34141 Korea)

Abstract ▼ AI-Helper

Remote functionalization of alkenes via chain walking has generally been limited to C(sp3)–H bonds α and β to polar-functional units, while γ-C(sp3)–H functionalization through controlled alkene transposition is a longstanding challenge. Herein, we describe NiH-catalyzed migratory formal hydroamination of alkenyl amides achieved via chelation-assisted control, whereby various amino groups are installed at the γ-position of aliphatic chains. By tuning olefin isomerization and migratory hydroamination through ligand and directing group optimization, γ-selective amination can be achieved via stabilization of a 6-membered nickellacycle by an 8-aminoquinoline directing group and subsequent interception by an aminating reagent. A range of amines can be installed at the γ-C(sp3)–H bond of unactivated alkenes with varying alkyl chain lengths, enabling late-stage access to value-added γ-aminated products. Moreover, by employing picolinamide-coupled alkene substrates, this approach is further extended to δ-selective amination. The chain-walking mechanism and pathway selectivity are investigated by experimental and computational methods.Sequential alkene isomerization and cross-coupling enables remote functionalization, but coupling has been limited to positions at a carbon chain terminus or proximal to a functional group. Here the authors show a method to interrupt isomerization with a nickellacycle, which enables coupling at an atypical, unreactive position.

참고문헌 (70)

1. Bergman RG C–H activation Nature 2007 446 391 393 10.1038/446391a 17377575

상세보기
2. Newhouse T Baran PS If C–H bonds could talk: selective C–H bond oxidation Angew. Chem. Int. Ed. 2011 50 3362 3374 10.1002/anie.201006368

상세보기
3. Dhungana RK Sapkota RR Niroula D Giri R Walking metals: catalytic difunctionalization of alkenes at nonclassical sites Chem. Sci. 2020 11 9757 9774 10.1039/D0SC03634J 34094239

상세보기
4. Sommer H Julia-Hernandez F Martin R Marek I Walking metals for remote functionalization ACS Cent. Sci. 2018 4 153 165 10.1021/acscentsci.8b00005 29532015

상세보기
5. Janssen‐Müller D Sahoo B Sun SZ Martin R Tackling remote sp 3 C−H functionalization via Ni‐catalyzed “chain‐walking” reactions Isr. J. Chem. 2019 60 195 206 10.1002/ijch.201900072

상세보기
6. Vasseur A Bruffaerts J Marek I Remote functionalization through alkene isomerization Nat. Chem. 2016 8 209 219 10.1038/nchem.2445 26892551

상세보기
7. Li Y Wu D Cheng HG Yin G Difunctionalization of alkenes involving metal Migr. Angew. Chem. Int. Ed. 2020 59 7990 8003 10.1002/anie.201913382

상세보기
8. Massad I Marek I Alkene isomerization through allylmetals as a strategic tool in stereoselective synthesis ACS Catal. 2020 10 5793 5804 10.1021/acscatal.0c01174

상세보기
9. Gao Y Visible-light-induced nickel-catalyzed cross-coupling with alkylzirconocenes from unactivated alkenes Chem 2020 6 675 688 10.1016/j.chempr.2019.12.010

상세보기
10. Sun SZ Borjesson M Martin-Montero R Martin R Site-selective Ni-catalyzed reductive coupling of α -haloboranes with unactivated olefins J. Am. Chem. Soc. 2018 140 12765 12769 10.1021/jacs.8b09425 30244574

상세보기
11. Sun SZ Romano C Martin R Site-selective catalytic deaminative alkylation of unactivated olefins J. Am. Chem. Soc. 2019 141 16197 16201 10.1021/jacs.9b07489 31565935

상세보기
12. Borah AJ Shi Z Rhodium-catalyzed, remote terminal hydroarylation of activated olefins through a long-range deconjugative isomerization J. Am. Chem. Soc. 2018 140 6062 6066 10.1021/jacs.8b03560 29727177

상세보기
13. Li J Qu S Zhao W Rhodium-catalyzed remote C(sp 3 )-H borylation of silyl enol ethers Angew. Chem. Int. Ed. 2020 59 2360 2364 10.1002/anie.201913281

상세보기
14. Zhou F Zhu J Zhang Y Zhu S NiH-catalyzed reductive relay hydroalkylation: a strategy for the remote C(sp 3 )-H alkylation of alkenes Angew. Chem. Int. Ed. 2018 57 4058 4062 10.1002/anie.201712731

상세보기
15. Gaide T Bianga J Schlipköter K Behr A Vorholt AJ Linear selective isomerization/hydroformylation of unsaturated fatty acid methyl esters: a bimetallic approach ACS Catal. 2017 7 4163 4171 10.1021/acscatal.7b00249

상세보기
16. Buslov I Song F Hu X An easily accessed nickel nanoparticle catalyst for alkene hydrosilylation with tertiary silanes Angew. Chem. Int. Ed. 2016 55 12295 12299 10.1002/anie.201606832

상세보기
17. Buslov I Becouse J Mazza S Montandon-Clerc M Hu X Chemoselective alkene hydrosilylation catalyzed by nickel pincer complexes Angew. Chem. Int. Ed. 2015 54 14523 14526 10.1002/anie.201507829

상세보기
18. Obligacion JV Chirik PJ Bis(imino)pyridine cobalt-catalyzed alkene isomerization-hydroboration: a strategy for remote hydrofunctionalization with terminal selectivity J. Am. Chem. Soc. 2013 135 19107 19110 10.1021/ja4108148 24328236

상세보기
19. Dupuy S Zhang KF Goutierre AS Baudoin O Terminal-selective functionalization of alkyl chains by regioconvergent cross-coupling Angew. Chem. Int. Ed. 2016 55 14793 14797 10.1002/anie.201608535

상세보기
20. Julia-Hernandez F Moragas T Cornella J Martin R Remote carboxylation of halogenated aliphatic hydrocarbons with carbon dioxide Nature 2017 545 84 88 10.1038/nature22316 28470192

상세보기
21. Xiao J He Y Ye F Zhu S Remote sp 3 C–H amination of alkenes with nitroarenes Chem 2018 4 1645 1657 10.1016/j.chempr.2018.04.008

상세보기
22. Zhang Y Xu X Zhu S Nickel-catalysed selective migratory hydrothiolation of alkenes and alkynes with thiols Nat. Commun. 2019 10 1752 10.1038/s41467-019-09783-w 30988306

상세보기
23. He Y Cai Y Zhu S Mild and regioselective benzylic C–H functionalization: Ni-catalyzed reductive arylation of remote and proximal olefins J. Am. Chem. Soc. 2017 139 1061 1064 10.1021/jacs.6b11962 28051861

상세보기
24. Zhang Y He J Song P Wang Y Zhu S Ligand-enabled NiH-catalyzed migratory hydroamination: chain walking as a strategy for regiodivergent/regioconvergent remote sp 3 C–H amination CCS Chem. 2020 2 2259 2268
25. Romano C Fiorito D Mazet C Remote functionalization of α , β -unsaturated carbonyls by multimetallic sequential catalysis J. Am. Chem. Soc. 2019 141 16983 16990 10.1021/jacs.9b09373 31587562

상세보기
26. Han C Palladium-catalyzed remote 1,n-arylamination of unactivated terminal alkenes ACS Catal. 2019 9 4196 4202 10.1021/acscatal.9b00688

상세보기
27. Kohler DG Gockel SN Kennemur JL Waller PJ Hull KL Palladium-catalysed anti-Markovnikov selective oxidative amination Nat. Chem. 2018 10 333 340 10.1038/nchem.2904 29461537

상세보기
28. Liu B Nickel-catalyzed remote and proximal Wacker-type oxidation Commun. Chem. 2019 2 5 10.1038/s42004-018-0107-y

상세보기
29. Lee WC Nickel-catalysed para-C–H activation of pyridine with switchable regioselective hydroheteroarylation of allylarenes Chem. Commun. 2015 51 17104 17107 10.1039/C5CC07455J

상세보기
30. Wang W Migratory arylboration of unactivated alkenes enabled by nickel catalysis Angew. Chem. Int. Ed. 2019 58 4612 4616 10.1002/anie.201814572

상세보기
31. Meng QY Schirmer TE Katou K Konig B Controllable isomerization of alkenes by dual visible-light-cobalt catalysis Angew. Chem. Int. Ed. 2019 58 5723 5728 10.1002/anie.201900849

상세보기
32. Chen X Cheng Z Guo J Lu Z Asymmetric remote C–H borylation of internal alkenes via alkene isomerization Nat. Commun. 2018 9 3939 10.1038/s41467-018-06240-y 30258070

상세보기
33. Scheuermann ML Johnson EJ Chirik PJ Alkene isomerization-hydroboration promoted by phosphine-ligated cobalt catalysts Org. Lett. 2015 17 2716 2719 10.1021/acs.orglett.5b01135 26010715

상세보기
34. Li Y Reaction scope and mechanistic insights of nickel-catalyzed migratory Suzuki-Miyaura cross-coupling Nat. Commun. 2020 11 417 10.1038/s41467-019-14016-1 31964876

상세보기
35. Zhou L Zhu C Bi P Feng C Ni-catalyzed migratory fluoro-alkenylation of unactivated alkyl bromides with gem-difluoroalkenes Chem. Sci. 2019 10 1144 1149 10.1039/C8SC04162H 30774912

상세보기
36. Yu R Rajasekar S Fang X Enantioselective nickel-catalyzed migratory hydrocyanation of nonconjugated dienes Angew. Chem. Int. Ed. 2020 59 21436 21441 10.1002/anie.202008854

상세보기
37. Matt C Kern C Streuff J Zirconium-catalyzed remote defunctionalization of alkenes ACS Catal. 2020 10 6409 6413 10.1021/acscatal.0c01605

상세보기
38. Romano C Mazet C Multicatalytic stereoselective synthesis of highly substituted alkenes by sequential isomerization/cross-coupling reactions J. Am. Chem. Soc. 2018 140 4743 4750 10.1021/jacs.8b02134 29561600

상세보기
39. Ebe Y Onoda M Nishimura T Yorimitsu H Iridium-catalyzed regio- and enantioselective hydroarylation of alkenyl ethers by olefin isomerization Angew. Chem. Int. Ed. 2017 56 5607 5611 10.1002/anie.201702286

상세보기
40. Yuan Q Sigman MS Palladium-catalyzed enantioselective relay heck arylation of enelactams: accessing α , β -unsaturated delta-lactams J. Am. Chem. Soc. 2018 140 6527 6530 10.1021/jacs.8b02752 29746119

상세보기
41. Qian D Hu X Ligand-controlled regiodivergent hydroalkylation of pyrrolines Angew. Chem. Int. Ed. 2019 58 18519 18523 10.1002/anie.201912629

상세보기
42. Hu M Ge S Versatile cobalt-catalyzed regioselective chain-walking double hydroboration of 1,n-dienes to access gem-bis(boryl)alkanes Nat. Commun. 2020 11 765 10.1038/s41467-020-14543-2 32034153

상세보기
43. Wang W Ding C Yin G Catalyst-controlled enantioselective 1,1-arylboration of unactivated olefins Nat. Catal. 2020 3 951 958 10.1038/s41929-020-00523-8

상세보기
44. Zhang C Santiago CB Kou L Sigman MS Alkenyl carbonyl derivatives in enantioselective redox relay Heck reactions: accessing α , β -unsaturated systems J. Am. Chem. Soc. 2015 137 7290 7293 10.1021/jacs.5b04289 26030059

상세보기
45. Ohlmann DM Goossen LJ Dierker M Regioselective synthesis of β-aryl- and β-amino-substituted aliphatic esters by rhodium-catalyzed tandem double-bond migration/conjugate addition Chem. Eur. J. 2011 17 9508 9519 10.1002/chem.201100654 21766361

상세보기
46. Yu X Site-selective alkene borylation enabled by synergistic hydrometallation and borometallation Nat. Catal. 2020 3 585 592 10.1038/s41929-020-0470-9

상세보기
47. Chen X Rao W Yang T Koh MJ Alkyl halides as both hydride and alkyl sources in catalytic regioselective reductive olefin hydroalkylation Nat. Commun. 2020 11 5857 10.1038/s41467-020-19717-6 33203895

상세보기
48. Jeon J Lee C Seo H Hong S NiH-catalyzed proximal-selective hydroamination of unactivated alkenes J. Am. Chem. Soc. 2020 142 20470 20480 10.1021/jacs.0c10333 33205955

상세보기
49. Shrestha B Ni-catalyzed regioselective 1,2-dicarbofunctionalization of olefins by intercepting heck intermediates as imine-stabilized transient metallacycles J. Am. Chem. Soc. 2017 139 10653 10656 10.1021/jacs.7b06340 28737904

상세보기
50. Liu Z Palladium(0)-catalyzed directed syn-1,2-carboboration and -silylation: alkene scope, applications in dearomatization, and stereocontrol by a chiral auxiliary Angew. Chem. Int. Ed. 2019 58 17068 17073 10.1002/anie.201910304

상세보기
51. van der Puyl VA Derosa J Engle KM Directed, nickel-catalyzed umpolung 1,2-carboamination of alkenyl carbonyl compounds ACS Catal. 2018 9 224 229 10.1021/acscatal.8b04516

상세보기
52. Yang KS Gurak JA Jr Liu Z Engle KM Catalytic, regioselective hydrocarbofunctionalization of unactivated alkenes with diverse C–H nucleophiles J. Am. Chem. Soc. 2016 138 14705 14712 10.1021/jacs.6b08850 27709911

상세보기
53. Wang H Palladium-catalyzed amide-directed enantioselective hydrocarbofunctionalization of unactivated alkenes using a chiral monodentate oxazoline ligand J. Am. Chem. Soc. 2018 140 3542 3546 10.1021/jacs.8b00641 29474067

상세보기
54. Lv H Xiao LJ Zhao D Zhou QL Nickel(0)-catalyzed linear-selective hydroarylation of unactivated alkenes and styrenes with aryl boronic acids Chem. Sci. 2018 9 6839 6843 10.1039/C8SC02101E 30310616

상세보기
55. Li Y Directed copper-catalyzed intermolecular aminative difunctionalization of unactivated alkenes J. Am. Chem. Soc. 2019 141 18475 18485 10.1021/jacs.9b07607 31600069

상세보기
56. Gurak JA Yang KS Liu Z Engle KM Directed, regiocontrolled hydroamination of unactivated alkenes via protodepalladation J. Am. Chem. Soc. 2016 138 5805 5808 10.1021/jacs.6b02718 27093112

상세보기
57. Li M Kwong FY Cobalt-catalyzed tandem C–H activation/C–C cleavage/C–H cyclization of aromatic amides with alkylidenecyclopropanes Angew. Chem. Int. Ed. 2018 57 6512 6516 10.1002/anie.201801706

상세보기
58. Rouquet G Chatani N Catalytic functionalization of C(sp 2 )–H and C(sp 3 )–H bonds by using bidentate directing groups Angew. Chem. Int. Ed. 2013 52 11726 11743 10.1002/anie.201301451

상세보기
59. Basnet P Ni-catalyzed regioselective β,δ-diarylation of unactivated olefins in ketimines via ligand-enabled contraction of transient nickellacycles: rapid access to remotely diarylated ketones J. Am. Chem. Soc. 2018 140 7782 7786 10.1021/jacs.8b03163 29893556

상세보기
60. Li W Boon JK Zhao Y Nickel-catalyzed difunctionalization of allyl moieties using organoboronic acids and halides with divergent regioselectivities Chem. Sci. 2018 9 600 607 10.1039/C7SC03149A 29629124

상세보기
61. Lv H Nickel-catalyzed intermolecular oxidative Heck arylation driven by transfer hydrogenation Nat. Commun. 2019 10 5025 10.1038/s41467-019-12949-1 31690717

상세보기
62. Yoo EJ Ma S Mei T-S Chan KSL Yu J-Q Pd-catalyzed intermolecular C–H amination with alkylamines J. Am. Chem. Soc. 2011 133 7652 7655 10.1021/ja202563w 21520961

상세보기
63. Zhu S Niljianskul N Buchwald SL Enantio- and regioselective CuH-catalyzed hydroamination of alkenes J. Am. Chem. Soc. 2013 135 15746 15749 10.1021/ja4092819 24106781

상세보기
64. Miki Y Hirano K Satoh T Miura M Copper-catalyzed intermolecular regioselective hydroamination of styrenes with polymethylhydrosiloxane and hydroxylamines Angew. Chem. Int. Ed. 2013 52 10830 10834 10.1002/anie.201304365

상세보기
65. Berman AM Johnson JS Copper-catalyzed electrophilic amination of diorganozinc reagents J. Am. Chem. Soc. 2004 126 5680 5681 10.1021/ja049474e 15125656

상세보기
66. Xie C Catalytic Aza-Wacker annulation: tuning mechanism by the activation mode of amide and enantioselective syntheses of melinonine‑E and strychnoxanthine Org. Lett. 2018 20 2386 2390 10.1021/acs.orglett.8b00725 29595983

상세보기
67. Niu D Buchwald SL Design of modified amine transfer reagents allows the synthesis of α -chiral secondary amines via CuH-catalyzed hydroamination J. Am. Chem. Soc. 2015 137 9716 9721 10.1021/jacs.5b05446 26144542

상세보기
68. Blackmond DG Kinetic profiling of catalytic organic reactions as a mechanistic tool J. Am. Chem. Soc. 2015 137 10852 10866 10.1021/jacs.5b05841 26285166

상세보기
69. Cornella J Gómez-Bengoa E Martin R Combined experimental and theoretical study on the reductive cleavage of inert C−O bonds with silanes: ruling out a classical Ni(0)/Ni(II) catalytic couple and evidence for Ni(I) intermediates J. Am. Chem. Soc. 2013 135 1997 2009 10.1021/ja311940s 23316793

상세보기
70. Saper NI Hartwig JF Mechanistic investigations of the hydrogenolysis of diaryl ethers catalyzed by nickel complexes of N-heterocyclic carbene ligands J. Am. Chem. Soc. 2017 139 17667 17676 10.1021/jacs.7b10537 29116776

상세보기

LOADING...

활용도 분석정보

상세보기

다운로드

내보내기

활용도 Top5 논문

해당 논문의 주제분야에서 활용도가 높은 상위 5개 콘텐츠를 보여줍니다.
더보기 버튼을 클릭하시면 더 많은 관련자료를 살펴볼 수 있습니다.

표제어: PCR

동의어: Packet Collision Rate

용어 설명 출처 목록 (6)

용어 설명: PCR은 세균 특이성이 있는 primer를 이용하여 적은 수의 세균이 있을지라도 쉽게 검출할 수 있는 유용한 방법이며, 이를 이용하여 구강 내 치면세균막이나 타액에서 직접 세균을 검출할 수 있게 되었다[8].

내보내기 구분	파일저장 인쇄 메일전송
구성항목	기본정보 상세정보 관리번호, 논문명, 저널/프로시딩명, 저자 , 발행년, 권, 호, 시작페이지, 끝페이지, 발행기관 관리번호, 논문명, 대등논문명, 저자 , 저널/프로시딩명, 발행기관, 발행년, 발행언어, 권, 호, 시작페이지, 끝페이지, ISBN, ISSN, 주제분야, 키워드, 초록(한글), 초록(영문), 저자(소속기관)
저장형식	Text(ASCII format) Excel format RefWorks Direct Export RIS format (for Reference Manager, ProCite, EndNote), Scholar's Aids, Mendeley
메일정보	받는사람 (필수) @ 보내는사람 (선택) @ 제목 내용 KISTI 검색결과 이메일 서비스
안내	총 건의 자료가 검색되었습니다. 다운받으실 자료의 인덱스를 입력하세요. (1-10,000) 검색결과의 순서대로 최대 10,000건 까지 다운로드가 가능합니다. 데이타가 많을 경우 속도가 느려질 수 있습니다.(최대 2~3분 소요) 다운로드 파일은 UTF-8 형태로 저장됩니다. 파일의 내용이 제대로 보이지 않을실 때는 웹브라우저 상단의 보기 -> 인코딩 -> 자동선택 여부를 확인하십시오. ~ Text(ASCII format) Excel format

연합인증