One-step synthesis of conjugated enynenitriles from ... S Supporting information for: One-step...

S1

Supportinginformationfor:

One-stepsynthesisofconjugatedenynenitrilesfrom

bromocyanoacetylene

RomainLigny,aEtienneS.Gauthier,aManuelYáñez,bThierryRoisnel,cJean-Claude

Guillemin,aY.Troleza*

aÉcoleNationaleSupérieuredeChimiedeRennes,UMR6226,CNRS,11AlléedeBeaulieu,CS50837,

35708RennesCedex7,France.Tel:33223238069

E-mail:[email protected]

bDepartamentodeQuímica,Módulo13,UniversidadAutónomadeMadrid,CampusdeExcelencia

UAM-CSIC,Cantoblanco,28049Madrid,Spain

c Centre de Diffractométrie X, Institut des Sciences Chimiques de Rennes, CNRS (UMR 6226),

UniversitédeRennes1,CampusdeBeaulieu,35042RennesCedex,France

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2017

S2

NMRSection...........................................................................................................................................3

1Hspectrumofcompound5(CDCl3,400MHz)...............................................................................313Cspectrumofcompound5(CDCl3,125MHz)..............................................................................31Hspectrumofcompound6(CDCl3,400MHz)...............................................................................413Cspectrumofcompound6(CDCl3,125MHz)..............................................................................41Hspectrumofcompound7(CDCl3,400MHz)...............................................................................513C{1H}spectrumofcompound7(CDCl3,125MHz)........................................................................51Hspectrumofcompound8(CDCl3,400MHz)...............................................................................613Cspectrumofcompound8(CDCl3,125MHz)..............................................................................61Hspectrumofcompound9(CDCl3,400MHz)...............................................................................713Cspectrumofcompound9(CDCl3,125MHz)..............................................................................71Hspectrumofcompound10(CDCl3,400MHz).............................................................................813Cspectrumofcompound10(CDCl3,125MHz)............................................................................81Hspectrumofcompound11(CDCl3,400MHz).............................................................................913Cspectrumofcompound11(CDCl3,125MHz)............................................................................91Hspectrumofcompound12(CDCl3,400MHz)...........................................................................1013Cspectrumofcompound12(CDCl3,125MHz)..........................................................................101Hspectrumofcompound14(CDCl3,400MHz)...........................................................................1113Cspectrumofcompound14(CDCl3,125MHz)..........................................................................111Hspectrumofcompound17(CDCl3,400MHz)...........................................................................1213Cspectrumofcompound17(CDCl3,125MHz)..........................................................................121Hspectrumofcompound18(CDCl3,400MHz)...........................................................................1313Cspectrumofcompound18(CDCl3,125MHz)..........................................................................131Hspectrumofcompound20(CDCl3,400MHz)...........................................................................1413Cspectrumofcompound20(CDCl3,125MHz)..........................................................................141Hspectrumofcompound21(CDCl3,400MHz)...........................................................................1513Cspectrumofcompound21(CDCl3,125MHz)..........................................................................151Hspectrumofcompound22(CDCl3,400MHz)...........................................................................1613Cspectrumofcompound22(CDCl3,125MHz)..........................................................................161Hspectrumofcompound23(CDCl3,400MHz)...........................................................................1713Cspectrumofcompound23(CDCl3,125MHz)..........................................................................171Hspectrumofcompound24(CDCl3,400MHz)...........................................................................18

TheoreticalcalculationsofE/Zconformersofenynessystems..........................................................19

S3

NMRSection1Hspectrumofcompound5(CDCl3,400MHz)

13Cspectrumofcompound5(CDCl3,125MHz)

S4

1Hspectrumofcompound6(CDCl3,400MHz)


S5


13C{1H}spectrumofcompound7(CDCl3,125MHz)

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S19

TheoreticalcalculationsofE/Zconformersofenynessystems

ModelZ ModelE

Gas-Phase

ModelZ ModelE Differences(kj/mol)

B3LYP/6-31+g(d,p)

Enthalpy -537.977805(a.u.) -537.982753(a.u.) 13.0

Freeenergy -538.035818 -538.041625 15.2

High-level(G4MP2)

Enthalpy -537.331187(a.u.) -537.335201 10.5

Freeenergy -537.335201 -537.394459 11.6

InTHF(B3lyp/6-31+G(d,p))

Enthalpy -537.987174 -537.995100 20.8

Freeenergy -538.045144 -538.054451 24.4

S20

ModelZ–B3LYP/6-31+G(d,p)calculations

Optimizedgeometry(cartesiancoordinatesinÅ)6-3.3208320.597983-0.1230116-2.5504851.4615130.6418667-4.6118980.1532510.0163226-5.185513-0.791826-0.9818156-6.366896-0.176319-1.7480876-5.535205-2.151216-0.3561301-4.395608-0.971771-1.7091051-6.0772810.769414-2.2156991-6.685303-0.863968-2.5387401-7.2353640.007715-1.1068861-4.665165-2.5835890.1468951-6.354039-2.0839350.3679031-5.852331-2.843142-1.1435586-5.5298410.5440561.1186386-5.9259492.0306901.0856046-5.0826370.0283012.4978061-6.446204-0.0035200.8894751-6.3138562.2979420.0979651-6.7208922.2006311.8199431-5.1073322.7046961.3328841-4.903874-1.0505442.4595361-4.1860400.5172312.8754641-5.8841490.2141573.2210666-2.5817470.104014-1.2640196-1.889181-0.257746-2.1896541-1.285663-0.581935-3.0072236-2.8190762.1822041.8234847-2.9394142.8186522.7973911-1.5452951.6210730.268761Enthalpy= -537.977805hartrees Freeenergy=-538.035818hartrees

S21

ModelE–B3LYP/6-31+G(d,p)calculationsOptimizedgeometry(cartesiancoordinatesinÅ)60.765850-0.111765-0.12386161.6256670.964855-0.21306911.2680361.981480-0.16158163.0233340.820341-0.37668374.1824230.762330-0.5116747-0.599649-0.0376510.0351036-1.418693-1.2729410.1185646-2.405700-1.393390-1.0534936-2.110862-1.4174911.4832911-0.713583-2.0988910.0287441-1.881136-1.332427-2.0116331-2.915744-2.361257-1.0052401-3.178590-0.617334-1.0323901-1.380391-1.3733982.2965471-2.866247-0.6428111.6545311-2.620527-2.3853701.5351466-1.3315471.2483670.1325706-1.2876562.082035-1.1619646-0.9902992.0574781.3981801-2.3745660.9472090.2509081-1.5984501.476924-2.0183691-1.9820202.924000-1.0700241-0.3002722.490467-1.3838651-1.0959391.4350112.29123710.0218142.4656471.3947731-1.6867902.8982511.48480361.362853-1.418132-0.20580761.943440-2.477610-0.28350212.470002-3.402735-0.353648Enthalpy= -537.982753hartrees Freeenergy=-538.041625hartrees

S22

ModelZ–G4MP2calculationsOptimizedgeometry(cartesiancoordinatesinÅ)6-0.1652941.091130-0.0002156-1.4908221.473623-0.00034370.430301-0.141720-0.00006161.909884-0.248707-0.00021762.442682-0.918230-1.27561362.443033-0.9168271.27576512.2823660.773794-0.00085512.081248-0.398159-2.16701813.536475-0.879179-1.27784212.154340-1.971289-1.35104812.082030-0.3956272.16668612.154470-1.9697291.35254413.536835-0.8780191.2775586-0.294985-1.4341030.0004816-1.087558-1.694592-1.2912066-1.087528-1.6934941.29240410.507860-2.1735740.0007951-0.446985-1.552543-2.1662421-1.432070-2.733846-1.2886811-1.966828-1.061068-1.3932981-0.446938-1.5506702.1673031-1.966823-1.0599201.3939881-1.432010-2.7327591.29077760.7107932.235730-0.00023461.3644793.246713-0.00021711.9498934.133312-0.0002236-2.6907380.743559-0.0004607-3.7332460.226709-0.0005671-1.6453622.545505-0.000401

Enthalpy= -537.331187hartreesFreeEnergy=-537.335201hartrees

S23

ModelE–G4MP2calculationsOptimizedgeometry(cartesiancoordinatesinÅ)

6-0.7629070.195193-0.0001076-1.714774-0.795555-0.0001151-1.445162-1.839008-0.0000156-3.098747-0.524750-0.0002257-4.247788-0.353318-0.00029870.5971090.004567-0.00000161.5194761.1600600.00016862.3744071.219865-1.27453962.3740611.2197641.27511010.8827692.0438690.00011011.7418451.220634-2.16645512.9674932.139637-1.27597713.0750490.381848-1.34916711.7412561.2205012.16685613.0746470.3817111.34987612.9671822.1395121.27676761.218792-1.3360240.00008760.954193-2.136452-1.28765460.953633-2.1365771.28763612.291035-1.1302060.00033211.236001-1.550167-2.16628111.561392-3.046955-1.2764321-0.088313-2.433726-1.40752511.234882-1.5503122.1664551-0.088886-2.4340401.40693911.560987-3.0469791.276664

S24

6-1.2495731.543904-0.0002056-1.7326432.645909-0.0002271-2.1729273.6129080.000382Enthalpy= -537.335201hartreesFreeEnergy=-537.394459hartreesModelZ–B3LYP/6-31+G(d,p)calculationsinTHFsolventOptimizedgeometry(cartesiancoordinatesinÅ)6-0.1667971.082805-0.0001896-1.5060811.466889-0.00023870.431509-0.143451-0.00005761.921731-0.250640-0.00020762.447524-0.920965-1.27799162.447863-0.9196061.27814612.2922870.772676-0.00082412.085716-0.400264-2.16958513.541479-0.879632-1.27911212.160072-1.974876-1.35063912.086428-0.3978502.16927612.160237-1.9733821.35206313.541825-0.8784631.2788686-0.295408-1.4414210.0004556-1.082022-1.694800-1.2969986-1.081991-1.6937851.29812110.505169-2.1822730.0007421-0.422809-1.594763-2.1641311-1.467548-2.719677-1.2801001-1.931905-1.026823-1.4297571-0.422755-1.5930632.1651591-1.931886-1.0257261.4303971-1.467501-2.7186791.28202760.7063052.236617-0.000280

S25

61.3553153.259526-0.00032811.9431624.151299-0.0003496-2.7098940.740618-0.0002797-3.7725400.246751-0.0003281-1.6679832.538979-0.000298 Enthalpy= -537.987174hartrees Freeenergy=-538.045144hartreesModelE–B3LYP/6-31+G(d,p)calculationsinTHFsolventOptimizedgeometry(cartesiancoordinatesinÅ)6-0.7588700.201113-0.0000546-1.718119-0.801637-0.0000811-1.451124-1.846697-0.0000086-3.100396-0.529979-0.0002067-4.259902-0.364006-0.00032470.5926860.0077170.00001061.5268891.1676530.00019162.3779871.217529-1.27742862.3775401.2174701.27810910.8945712.0546290.00009311.7437401.219284-2.16884112.9719192.137101-1.27869413.0761260.377152-1.34965411.7429781.2192612.16929813.0755860.3770361.35057312.9715412.1369981.27959561.220114-1.3416000.00000660.955897-2.140348-1.28899060.955719-2.1405421.28885312.290118-1.1290110.000114

S26

11.197929-1.539354-2.17000711.600439-3.025240-1.2931021-0.075518-2.483821-1.38724011.197068-1.5394862.1700141-0.075551-2.4845801.38664411.600719-3.0251001.2931846-1.2493141.555523-0.0001266-1.7409042.662307-0.0001931-2.1692893.640925-0.000256Enthalpy= -537.995100hartrees Freeenergy=-538.054451hartrees

Compound6,isomerZ Compound6,isomerE

Gas-Phase

IsomerZ IsomerE Differences(kj/mol)

B3LYP/6-31+g(d,p)

Enthalpy -768.972698(a.u.) -768.979158(a.u.) 17.0

S27

Freeenergy -769.044194 -769.050500 16.5

S28

Compound6,IsomerZ–B3LYP/6-31+G(d,p)calculations

Optimizedgeometry(cartesiancoordinatesinÅ)61.031393-0.6264510.07524561.358378-1.9758180.05673271.8258920.4961250.09958061.1954681.8328480.27742661.1762052.642800-1.02878161.8143712.6195141.44371610.1598241.6357610.55222510.6743022.083995-1.82422310.6332843.581744-0.87500412.1837762.900234-1.37235411.7854462.0360022.36859112.8511242.9157561.25387011.2382663.5372501.60236863.2871880.514122-0.17748963.660923-0.121583-1.52744064.1495650.0390811.00583413.5065631.577945-0.29295013.0472820.299522-2.33004014.7093760.109918-1.74394813.559953-1.205944-1.54315313.8914980.5924301.91320514.050300-1.0264471.20747415.2037070.2339640.7784656-0.393680-0.4165300.0592126-1.607995-0.3394480.02767662.595008-2.6479410.12055873.566269-3.2980970.17354010.510001-2.6485390.0059176-3.031430-0.245036-0.0038936-3.824772-1.4017620.1438216-3.6666521.001135-0.1838716-5.214907-1.3093190.1121441-3.340657-2.3630020.2825386-5.0573761.083767-0.2131011-3.0618471.894611-0.3012276-5.835772-0.068837-0.0655991-5.815043-2.2070950.2266211-5.5351802.049011-0.3524541-6.919262-0.000686-0.089584

S29

Enthalpy= -768.972698hartrees Freeenergy=-769.044194hartreesCompound6,IsomerE–B3LYP/6-31+G(d,p)calculationsOptimizedgeometry(cartesiancoordinatesinÅ)6-1.1812180.5841520.0577966-1.4397651.9415150.1446681-2.4454382.3308190.1703286-0.4062662.9039070.20525470.4198983.7294670.2570617-2.134717-0.407621-0.0045986-1.728135-1.831119-0.0958856-2.176192-2.479036-1.4157836-2.172046-2.6413141.1326101-0.637969-1.821662-0.0971201-1.812138-1.905652-2.2734721-1.767817-3.492899-1.4848321-3.265893-2.561964-1.4926731-1.804966-2.1813732.0549111-3.261534-2.7332931.2019131-1.763895-3.6557471.0711306-3.591142-0.1351410.0149536-4.0932060.625268-1.2271996-4.0893840.4607771.3452941-4.044735-1.126728-0.0478231-3.7687430.120471-2.1417171-5.1882770.643667-1.2186351-3.7446671.658369-1.2756621-3.763187-0.1568872.1870371-3.7395761.4789621.5243311-5.1844530.4809121.34201160.1988170.2002660.03212561.4029180.0257120.02006562.820958-0.1239150.00933563.6388521.0234360.08159263.421133-1.396629-0.07204965.0259820.8908330.07202613.1733152.0019400.14423664.809555-1.516617-0.08083612.793316-2.280387-0.12769365.615130-0.375436-0.008963

S30

15.6488441.7786090.12797215.263842-2.501088-0.14376416.696794-0.472719-0.016052Enthalpy= -768.979158hartreesFreeenergy=-769.050500hartrees

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