Supplementary Information SIJ. Braz. Chem. Soc., Vol. 27, No. 1, S1-S22, 2016.

Printed in Brazil - ©2016 Sociedade Brasileira de Química0103 - 5053 $6.00+0.00

*e-mail: millercrotti@ffclrp.usp.br#These authors contributed equally to this work.

Detailed 1H and 13C NMR Spectral Data Assignment for Two Dihydrobenzofuran Neolignans

Talita C. T. Medeiros,a,# Herbert J. Dias,a,# Eliane O. Silva,a Murilo J. Fukui,b Ana Carolina F. Soares,b Tapas Kar,c Vladimir C. G. Heleno,b Paulo M. Donate,a

Renato L. T. Parreirab and Antônio E. M. Crotti*,a

aDepartamento de Química, Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto, Universidade de São Paulo, 14040-901 Ribeirão Preto-SP, Brazil

bNúcleo de Pesquisas em Ciências Exatas e Tecnológicas, Universidade de Franca, 14404-600 Franca-SP, Brazil

cDepartment of Chemistry and Biochemistry, Utah State University, 84322-0300 Logan-UT, United States

(±)-trans-Dehydrodicoumarate dimethyl ester (2a)Yellow powder (yield: 36%); [α]D

25 0° (c 10.0, acetone); IR (KBr pellet) ν / cm−1: 3384, 2955, 1715, 1602, 1490, 1440, 1240, 1115, 982, 853. 1H NMR (400 MHz, CDCl3): d 3.81 (s, 3H, H10’), 3.83 (s, 3H, H10), 4.27 (dd, 1H, J 1.4, 7.2 Hz, H8), 6.09 (dt, 1H, J 0.6, 7.2 Hz, H7), 6.32 (d, 1H, J 15.9 Hz, H8’), 6.84 (dd, 2H, J 0.3, 8.3 Hz, H5), 6.89 (dd, 1H, J 0.4, 8.3 Hz, H3’), 7.27 (ddd, 2H, J 0.3, 0.6, 8.3 Hz, H2=H6), 7.43 (ddd, 1H, J 1.1, 2.0, 8.3 Hz, H2’), 7.55 (dddd, 1H, J 0.4, 0.7, 1.4, 2.0 Hz, H6’), 7.66 (ddd, 1H, J 1.1, 15.9 Hz, H7’); 13C NMR (100 MHz, CDCl3), DEPT 135, gHMQC and gHMBC: d 51.7, 52.9, 55.1, 87.7, 110.3, 115.2, 115.7, 124.9, 125.1, 127.5, 127.8, 130.8, 144.7, 146.1, 161.2, 167.9, 179.9 (s, C9); HRMS (TOF-ESI) m/z calcd. for C20H17O6

– [M – H]–: 353.1030, found: 353.1027.

[±)-trans-Dehydrodiferulate dimethyl ester (2b)Brownish oil (yield: 43%); [α]D

25 0° (c 10.0, acetone); IR (KBr pellet) ν / cm−1: 3395, 2951, 1740, 1723, 1644, 1594, 1523, 1432, 1269, 1165, 1140, 1095, 1036, 982, 941, 853. 1H NMR (400 MHz, CDCl3): δ 3.73 (s, 3H, H10’), 3.81 (s, 3H, H10), 3.84 (s, 3H, H11), 3.92 (s, 3H, H11’), 4.47 (dd, 1H, J 1.4, 7.3, H8), 6.04 (ddd, 1H, J 0.6, 0.8, 7.3 Hz, H7), 6.44 (d, 1H, J 15.8 Hz, H8’), 6.84 (dd, 1H, J 0.3, 8.3 Hz, H5), 6.92 (ddd, 1H, J 0.6, 2.1, 8.3, Hz H6), 7.10 (ddd, 1H, J 0.3, 0.8, 2.1 Hz, H2), 7.29 (ddd, 1H, J 0.8,

1.4, 2.6 Hz, H6’), 7.33 (dd, 1H, J 0.4, 2.6 Hz, H2’), 7.63 (ddd, 1H, J 0.4, 0.8, 15.8 Hz, H7’); 13C NMR (100 MHz, acetone-d6), DEPT 135, gHMQC and gHMBC: d 111.2, 113.9, 116.3, 116.8, 119.5, 120.7, 127.8, 129.9, 132.5, 145.9, 146.3, 148.5, 149.1, 151.5, 168.2, 172.1, 52.1, 53.5, 56.4, 56.8, 57.0, 88.8; HRMS (TOF-ESI) m/z calcd. for C22H21O8

– [M – H]–: 413.1240, found: 413.1241.

Detailed 1H and 13C NMR Spectral Data Assignment for Two Dihydrobenzofuran Neolignans J. Braz. Chem. Soc.S2

Figure S1. IR spectrum (KBr) of compound 2a.

Figure S2. ESI-Q-TOF of compound 2a.

Medeiros et al. S3Vol. 27, No. 1, 2016

Figure S3. 1H NMR spectrum (400 MHz, CDCl3, TMS) of compound 2a.

Figure S4. 1H NMR spectrum (400 MHz, acetone-d6, TMS) of compound 2a.

Detailed 1H and 13C NMR Spectral Data Assignment for Two Dihydrobenzofuran Neolignans J. Braz. Chem. Soc.S4

Figure S6. DEPT 135 (100 MHz, CDCl3, TMS) of compound 2a.

Figure S5. 13C NMR spectrum (100 MHz, CDCl3, TMS) of compound 2a.

Medeiros et al. S5Vol. 27, No. 1, 2016

Figure S8. DEPT 135 (100 MHz, acetone-d6, TMS) of compound 2a.

Figure S7. 13C NMR spectrum (100 MHz, acetone-d6, TMS) of compound 2a.

Detailed 1H and 13C NMR Spectral Data Assignment for Two Dihydrobenzofuran Neolignans J. Braz. Chem. Soc.S6

Figure S10. gHMQC spectrum (400 MHz, CDCl3, TMS) of compound 2a.

Figure S9. 1H-1H gCOSY spectrum (400 MHz, CDCl3, TMS) of compound 2a.

Medeiros et al. S7Vol. 27, No. 1, 2016

Figure S12. J-resolved spectrum (400 MHz, CDCl3, TMS) of compound 2a.

Figure S11. gHMBC spectrum (400 MHz, CDCl3, TMS) of compound 2a.

Detailed 1H and 13C NMR Spectral Data Assignment for Two Dihydrobenzofuran Neolignans J. Braz. Chem. Soc.S8

Figure S14. HR-ESI-MS spectrum of compound 2b.

Figure S13. NOESY spectrum (400 MHz, CDCl3, TMS) of compound 2a.

Medeiros et al. S9Vol. 27, No. 1, 2016

Figure S16. 1H NMR spectrum (400 MHz, CDCl3, TMS) of compound 2b.

Figure S15. IR spectrum (KBr) of compound 2b.

Detailed 1H and 13C NMR Spectral Data Assignment for Two Dihydrobenzofuran Neolignans J. Braz. Chem. Soc.S10

Figure S18. 13C NMR spectrum (100 MHz, CDCl3, TMS) of compound 2b.

Figure S17. 1H NMR spectrum (400 MHz, acetone-d6, TMS) of compound 2b.

Medeiros et al. S11Vol. 27, No. 1, 2016

Figure S20. DEPT 135 (100 MHz, acetone-d6, TMS) of compound 2b.

Figure S19. 13C NMR spectrum (100 MHz, acetone-d6, TMS) of compound 2b.

Detailed 1H and 13C NMR Spectral Data Assignment for Two Dihydrobenzofuran Neolignans J. Braz. Chem. Soc.S12

Figure S22. gHMQC spectrum (400 MHz, acetone-d6, TMS) of compound 2b.

Figure S21. 1H-1H gCOSY spectrum (400 MHz, acetone-d6, TMS) of compound 2b.

Medeiros et al. S13Vol. 27, No. 1, 2016

Figure S24. J-resolved spectrum (400 MHz, acetone-d6, TMS) of compound 2b.

Figure S23. gHMBC spectrum (400 MHz, acetone-d6, TMS) of compound 2b.

Detailed 1H and 13C NMR Spectral Data Assignment for Two Dihydrobenzofuran Neolignans J. Braz. Chem. Soc.S14

Figure S26. HR-ESI-MS spectrum of compound 2b.

Figure S25. NOESY spectrum (400 MHz, acetone-d6, TMS) of compound 2b.

Medeiros et al. S15Vol. 27, No. 1, 2016

Computational methods

XYZ coordinates of optimized structures and thermochemical parameters (B3LYP/6-311 + G(2d,p) level of theory).

a. trans Isomers-2a

6 −2.521532000 −0.312378000 0.0762710006 −2.295203000 −1.643012000 0.4717920006 −1.026344000 −2.118623000 0.7629620006 0.039376000 −1.233718000 0.6477760006 −0.144554000 0.087063000 0.2469970006 −1.414204000 0.550860000 −0.0332040008 1.330828000 −1.556070000 0.8898480006 2.108622000 −0.316508000 0.9117670006 1.227333000 0.733420000 0.1704750006 1.296393000 2.103999000 0.8418570008 1.503086000 2.243406000 2.0167450008 1.079400000 3.203384000 0.0850220006 0.962643000 3.149945000 −1.3449720006 −3.841978000 0.218539000 −0.2283120006 −5.026092000 −0.413111000 −0.1722950006 −6.256098000 0.321234000 −0.5405750008 −7.451916000 −0.325799000 −0.4439650006 −7.550397000 −1.672860000 0.0231460008 −6.266838000 1.464978000 −0.9272140006 3.472924000 − 0.540687000 0.3256010006 3.652685000 −1 .272707000 −0.8514640006 4.911279000 −1. 436218000 −1.4070590006 6.020529000 −0.858031000 −0.7906360006 5.859118000 −0.127250000 0.3827980006 4.591796000 0.020861000 0.9359510008 7.237794000 −1.048769000 −1.3819130001 −3.133131000 −2.322780000 0.561747000

1 −0.861891000 −3.140792000 1.0778800001 −1.581415000 1.581039000 −0.3269790001 2.189577000 −0.012466000 1.9561190001 1.546017000 0.805299000 −0.8710280001 0.716401000 4.164904000 −1.6472880001 0.166167000 2.478112000 −1.6662190001 1.909255000 2.858284000 −1.8028560001 −3.874008000 1.258093000 −0.5426610001 −5.094017000 −1.446148000 0.1363660001 −8.613071000 −1.905355000 0.0124510001 −7.174512000 −1.772844000 1.0436020001 −7.028202000 −2.366862000 −0.6392100001 2.798990000 −1.739264000 −1.3284730001 5.054070000 −2.012832000 −2.3122330001 6.720419000 0.317000000 0.8712790001 4.476882000 0.583617000 1.8554770001 7.925853000 −0.620948000 −0.859419000

Zero-point correction = 0.342553 (Hartree/Particle)Thermal correction to energy = 0.366500Thermal correction to enthalpy = 0.367444Thermal correction to Gibbs free energy = 0.285214Sum of electronic and zero-point energies = −1224.317563Sum of electronic and thermal energies = −1224.293616Sum of electronic and thermal enthalpies = −1224.292672Sum of electronic and thermal free energies = −1224.374902

Detailed 1H and 13C NMR Spectral Data Assignment for Two Dihydrobenzofuran Neolignans J. Braz. Chem. Soc.S16

6 2.503906000 −0.294305000 0.0758520006 2.273357000 −1.296350000 1.0368710006 1.003940000 −1.583154000 1.5141440006 −0.058481000 −0.838889000 1.0124650006 0.134074000 0.156496000 0.0613600006 1.400351000 0.431154000 −0.4128920008 −1.352535000 −1.012775000 1.3681170006 −2.145808000 0.072233000 0.7753580006 −1.224854000 0.723044000 −0.3026970006 −1.212429000 2.241558000 −0.3592640008 −0.976461000 2.858147000 −1.3676580008 −1.440080000 2.818757000 0.8334720006 −1.360434000 4.258335000 0.8548480006 3.826274000 0.030345000 −0.4383570006 5.003944000 −0.530386000 −0.1158800006 6.241500000 −0.042898000 −0.7611310008 7.425451000 −0.627930000 −0.4185810006 7.498790000 −1.689299000 0.5352060008 6.272297000 0.846584000 −1.5767710006 −3.455925000 −0.463284000 0.2722760006 −3.509394000 −1.538604000 −0.6202250006 −4.718847000 −2.013942000 −1.0972030006 −5.909172000 −1.411413000 −0.6891010006 −5.875591000 −0.342265000 0.2004620006 −4.653148000 0.118693000 0.6783780008 −7.073270000 −1.918847000 −1.1930130001 3.109016000 −1.864867000 1.425281000

1 0.837000000 −2.354439000 2.2546570001 1.552765000 1.201939000 −1.1602190001 −2.324795000 0.788401000 1.5765580001 −1.511502000 0.399075000 −1.3056060001 −1.580058000 4.544677000 1.8798480001 −2.088663000 4.686811000 0.1676040001 −0.360811000 4.583112000 0.5691250001 3.864837000 0.827478000 −1.1755610001 5.061128000 −1.330369000 0.6078430001 8.553806000 −1.946702000 0.6009070001 6.938731000 −2.566672000 0.2042740001 7.148746000 −1.370291000 1.5194260001 −2.592627000 −2.023060000 −0.9357100001 −4.761838000 −2.850604000 −1.7829100001 −6.799164000 0.124917000 0.5267720001 −4.637649000 0.945739000 1.3795530001 −7.824452000 −1.429055000 −0.839173000

Zero-point correction = 0.342445 (Hartree/Particle)Thermal correction to energy = 0.366589Thermal correction to enthalpy = 0.367533Thermal correction to Gibbs free energy = 0.283264Sum of electronic and zero-point energies = − 1224.329697Sum of electronic and thermal energies = −1224.305554Sum of electronic and thermal enthalpies = −1224.304609Sum of electronic and thermal free energies = −1224.388878

Medeiros et al. S17Vol. 27, No. 1, 2016

6 −2.700362000 −0.189260000 −0.2466940006 −2.476486000 −1.576605000 −0.1705540006 −1.206729000 −2.124294000 −0.2623330006 −0.140372000 −1.250308000 −0.4343680006 −0.321716000 0.124569000 −0.5070470006 −1.590133000 0.659328000 −0.4122220008 1.158031000 −1.631764000 −0.5378070006 1.923377000 −0.478599000 −0.9923660006 1.035483000 0.777395000 −0.6327340006 1.442219000 1.468438000 0.6749640008 1.094354000 1.064344000 1.7505940008 2.227042000 2.569249000 0.6191610006 2.705224000 3.121330000 −0.6138070006 −4.022802000 0.412614000 −0.1611240006 −5.203924000 −0.198517000 0.0286220006 −6.440321000 0.610683000 0.0767980008 −7.622657000 −0.025480000 0.3169420006 −7.690685000 −1.432147000 0.5594770008 −6.471029000 1.806422000 −0.0877990006 3.331375000 −0.554601000 −0.4739990006 3.609671000 −0.838533000 0.8673780006 4.915070000 −0.904803000 1.3239090006 5.973329000 −0.685325000 0.4428260006 5.714944000 −0.409798000 −0.8971180006 4.399953000 −0.355023000 −1.3456240008 7.238967000 −0.762338000 0.9499490001 −3.317871000 −2.246182000 −0.043682000

1 −1.043964000 −3.192641000 −0.2073670001 −1.745261000 1.731897000 −0.4523210001 1.946091000 −0.538086000 −2.0848270001 1.075269000 1.478229000 −1.4641730001 3.358501000 3.941068000 −0.3239020001 1.884966000 3.516789000 −1.2164140001 3.281150000 2.390530000 −1.1821870001 −4.058507000 1.493839000 −0.2614530001 −5.264757000 −1.270543000 0.1467610001 −8.741308000 −1.642543000 0.7479420001 −7.107350000 −1.717255000 1.4375730001 −7.363939000 −2.006173000 −0.3105340001 2.795728000 −1.011567000 1.5586920001 5.132187000 −1.126020000 2.3610840001 6.534764000 −0.255173000 −1.5911730001 4.210493000 −0.166082000 −2.3972230001 7.883435000 −0.602812000 0.250954000

Zero-point correction = 0.342336 (Hartree/Particle)Thermal correction to energy = 0.366263Thermal correction to enthalpy = 0.367208Thermal correction to Gibbs free energy = 0.285497Sum of electronic and zero-point energies = −1224.312567Sum of electronic and thermal energies = −1224.288640Sum of electronic and thermal enthalpies = −1224.287696Sum of electronic and thermal free energies = −1224.369407

b. cis Isomers-2a

Detailed 1H and 13C NMR Spectral Data Assignment for Two Dihydrobenzofuran Neolignans J. Braz. Chem. Soc.S18

6 −2.700376000 −0.189263000 0.2474800006 −2.476528000 −1.576651000 0.1720260006 −1.206746000 −2.124287000 0.2638150006 −0.140373000 −1.250199000 0.4351860006 −0.321694000 0.124702000 0.5073870006 −1.590141000 0.659400000 0.4124960008 1.158102000 −1.631588000 0.5384640006 1.923449000 −0.478314000 0.9926290006 1.035495000 0.777585000 0.6327440006 1.442185000 1.468261000 −0.6751370008 1.094007000 1.064081000 −1.7506390008 2.227593000 2.568685000 −0.6196920006 2.705319000 3.121497000 0.6131170006 −4.022824000 0.412591000 0.1616390006 −5.203876000 −0.198558000 −0.0284630006 −6.440300000 0.610595000 −0.0767420008 −7.622565000 −0.025523000 −0.3174190006 −7.690375000 −1.431895000 −0.5618120008 −6.471098000 1.806268000 0.0883540006 3.331398000 −0.554454000 0.4740850006 3.609395000 −0.839063000 −0.8672030006 4.914701000 −0.905465000 −1.3240000006 5.973129000 −0.685448000 −0.4432650006 5.715025000 −0.409191000 0.8965870006 4.400129000 −0.354285000 1.3453690008 7.238672000 −0.762672000 −0.9506110001 −3.317960000 −2.246298000 0.045827000

1 −1.043982000 −3.192667000 0.2094480001 −1.745262000 1.731991000 0.4521240001 1.946308000 −0.537491000 2.0851140001 1.075297000 1.478614000 1.4640210001 3.358690000 3.941076000 0.3229530001 3.281074000 2.391054000 1.1821470001 1.884839000 3.517295000 1.2152010001 −4.058571000 1.493812000 0.2620280001 −5.264642000 −1.270572000 −0.1467370001 −8.740788000 −1.641993000 −0.7518000001 −7.364695000 −2.007008000 0.3078930001 −7.106014000 −1.715954000 −1.4395590001 2.795297000 −1.012501000 −1.5582360001 5.131599000 −1.127194000 −2.3611130001 6.534995000 −0.254055000 1.5903540001 4.210898000 −0.164795000 2.3969130001 7.883274000 −0.602661000 −0.251849000

Zero-point correction = 0.342335 (Hartree/Particle)Thermal correction to energy = 0.366262Thermal correction to enthalpy = 0.367206Thermal correction to Gibbs free energy = 0.285506Sum of electronic and zero-point energies = −1224.312568Sum of electronic and thermal energies = −1224.288641Sum of electronic and thermal enthalpies = −1224.287697Sum of electronic and thermal free energies = −1224.369397

Medeiros et al. S19Vol. 27, No. 1, 2016

6 −2.806595000 −0.034456000 −0.0406430006 −2.587663000 −1.227689000 0.6675300006 −1.346308000 −1.572137000 1.1844990006 −0.290258000 −0.673866000 0.9737910006 −0.490771000 0.520218000 0.2922800006 −1.729430000 0.849791000 −0.2215930008 0.995557000 −0.882511000 1.3533720006 1.751602000 0.350462000 1.1122310006 0.850478000 1.223367000 0.1955100006 0.794285000 2.673386000 0.6522480008 1.117451000 3.080487000 1.7393670008 0.312949000 3.455537000 −0.3292200006 0.159155000 4.852018000 −0.0011850008 −1.217984000 −2.786048000 1.7944530006 −0.501582000 −2.836257000 3.0363300006 −4.102038000 0.333712000 −0.5932390006 −5.245760000 −0.370222000 −0.5666590006 −6.459961000 0.191804000 −1.1950190008 −7.604736000 −0.549175000 −1.1711120006 −7.657223000 −1.844862000 −0.5698790008 −6.504086000 1.272754000 −1.7316590006 3.113771000 0.024287000 0.5685860006 3.271903000 −0.844430000 −0.5134030006 4.523638000 −1.126088000 −1.0396110006 5.659699000 −0.526264000 −0.4690570006 5.506384000 0.348609000 0.5994400006 4.244676000 0.616991000 1.1200080008 6.882251000 −0.852143000 −0.9875290008 4.624570000 −2.050265000 −2.0459770006 5.084427000 −1.561270000 −3.3119160001 −3.394910000 −1.929114000 0.834318000

1 −1.873808000 1.774451000 −0.7665360001 1.848021000 0.852645000 2.0756590001 1.206016000 1.216811000 −0.8380860001 −0.239714000 5.316884000 −0.8985440001 1.123368000 5.284605000 0.2623410001 −0.530360000 4.969314000 0.8338260001 −0.649755000 −3.844485000 3.4177530001 −0.916579000 −2.113638000 3.7447890001 0.560914000 −2.643652000 2.8930790001 −4.146134000 1.297709000 −1.0920240001 −5.290518000 −1.341365000 −0.0958660001 −8.680454000 −2.186942000 −0.7097390001 −7.439968000 −1.800832000 0.4995620001 −6.977804000 −2.544145000 −1.0618860001 2.418721000 −1.344982000 −0.9553240001 6.385003000 0.807341000 1.0425020001 4.146940000 1.290734000 1.9630960001 7.572538000 −0.402097000 −0.4871190001 5.071144000 −2.416685000 −3.9847250001 6.097916000 −1.164601000 −3.2412330001 4.407072000 −0.789666000 −3.690903000

Zero-point correction = 0.406493 (Hartree/Particle)Thermal correction to energy = 0.436321Thermal correction to enthalpy = 0.437265Thermal correction to Gibbs free energy = 0.340606Sum of electronic and zero-point energies = −1453.374109Sum of electronic and thermal energies = −1453.344282Sum of electronic and thermal enthalpies = −1453.343338Sum of electronic and thermal free fnergies = −1453.439997

c. trans Isomers-2b

Detailed 1H and 13C NMR Spectral Data Assignment for Two Dihydrobenzofuran Neolignans J. Braz. Chem. Soc.S20

6 2.802877000 −0.041670000 −0.0414880006 2.544724000 −1.196107000 0.7164890006 1.288945000 −1.484271000 1.2314620006 0.258757000 −0.570481000 0.9677190006 0.497559000 0.586385000 0.2366120006 1.750754000 0.860305000 −0.2751450008 −1.034857000 −0.731001000 1.3410970006 −1.761861000 0.505414000 1.0258330006 −0.823122000 1.319941000 0.0935560006 −0.734018000 2.783384000 0.5007130008 −1.062491000 3.236551000 1.5678800008 −0.216160000 3.516766000 −0.4991590006 −0.032104000 4.920073000 −0.2194230008 1.114953000 −2.666394000 1.8930010006 0.435698000 −2.621476000 3.1556110006 4.113400000 0.268578000 −0.5936860006 5.237673000 −0.463329000 −0.5251040006 6.472881000 0.041207000 −1.1613830008 7.595100000 −0.731769000 −1.1026940006 7.602569000 −2.010419000 −0.4640150008 6.553211000 1.101842000 −1.7331230006 −3.116096000 0.177786000 0.4647460006 −3.256866000 −0.680891000 −0.6280710006 −4.500462000 −0.964245000 −1.1711090006 −5.645277000 −0.364909000 −0.6175440006 −5.512274000 0.480756000 0.4767790006 −4.258215000 0.747518000 1.0167900008 −6.851970000 −0.640859000 −1.1973110008 −4.573571000 −1.757847000 −2.2856000006 −5.207346000 −3.031561000 −2.1110660001 3.331117000 −1.910124000 0.924735000

1 1.925290000 1.755863000 −0.8585740001 −1.871429000 1.050086000 1.9642130001 −1.163075000 1.287274000 −0.9446730001 0.388469000 5.342466000 −1.1277870001 0.650247000 5.050779000 0.6195010001 −0.988585000 5.384675000 0.0161730001 0.516453000 −3.625453000 3.5674260001 −0.612958000 −2.350909000 3.0359610001 0.927419000 −1.911490000 3.8268890001 4.188514000 1.209387000 −1.1315480001 5.252035000 −1.415431000 −0.0149420001 8.614697000 −2.389554000 −0.5883790001 6.902821000 −2.701229000 −0.9391440001 7.382272000 −1.928362000 0.6025960001 −2.394060000 −1.156970000 −1.0786390001 −6.397371000 0.939069000 0.9071490001 −4.174384000 1.409532000 1.8705890001 −7.547165000 −0.158816000 −0.7349160001 −5.157699000 −3.525178000 −3.0798080001 −6.249558000 −2.918635000 −1.8093210001 −4.665925000 −3.627229000 −1.369876000

Zero-point correction = 0.406450 (Hartree/Particle)Thermal correction to energy = 0.436289Thermal correction to enthalpy = 0.437233Thermal correction to Gibbs free energy = 0.340656Sum of electronic and zero-point energies = −1453.374369Sum of electronic and thermal energies = −1453.344531Sum of electronic and thermal enthalpies = −1453.343586Sum of electronic and thermal free energies = −1453.440164

Medeiros et al. S21Vol. 27, No. 1, 2016

6 3.116107000 −0.187463000 −0.2176390006 2.851164000 1.181717000 −0.3871190006 1.572262000 1.671587000 −0.6132000006 0.531204000 0.738142000 −0.6763820006 0.765308000 −0.615884000 −0.4842520006 2.041173000 −1.091317000 −0.2575640008 −0.773445000 1.033702000 −0.9339460006 −1.446173000 −0.223259000 −1.2365010006 −0.563563000 −1.334618000 −0.5555400006 −1.047137000 −1.735753000 0.8442860008 −0.808631000 −1.075435000 1.8180600008 −1.773780000 −2.867600000 0.9894470006 −2.129805000 −3.709283000 −0.1145240008 1.417200000 3.009376000 −0.8399440006 0.393558000 3.683064000 −0.0933430006 4.455074000 −0.714781000 0.0037980006 5.608640000 −0.034182000 0.1023520006 6.871092000 −0.772069000 0.3208670008 8.023960000 −0.057340000 0.4615050006 8.037227000 1.371780000 0.4429670008 6.947739000 −1.975689000 0.3792930006 −2.907124000 −0.130486000 −0.8984400006 −3.349916000 0.380504000 0.3243040006 −4.701789000 0.459215000 0.6253350006 −5.645888000 0.001141000 −0.3100450006 −5.211370000 −0.492581000 −1.5344860006 −3.853897000 −0.551181000 −1.8289490008 −6.966242000 0.060152000 0.0350530008 −5.077793000 0.907509000 1.8619840006 −5.798819000 2.145415000 1.8963210001 3.652660000 1.908637000 −0.360275000

1 2.225082000 −2.148676000 −0.1066550001 −1.344753000 −0.370347000 −2.3161940001 −0.523694000 −2.198699000 −1.2151160001 −2.770036000 −4.479140000 0.3099990001 −1.248893000 −4.182117000 −0.5535680001 −2.687759000 −3.159243000 −0.8729190001 0.509791000 4.740099000 −0.3241390001 0.538140000 3.524237000 0.9788520001 −0.600771000 3.346091000 −0.3856110001 4.528127000 −1.794219000 0.1012780001 5.628005000 1.043044000 0.0242530001 9.075196000 1.653111000 0.6075620001 7.423837000 1.789700000 1.2439430001 7.711599000 1.764730000 −0.5227580001 −2.645470000 0.721899000 1.0710800001 −5.941263000 −0.830031000 −2.2638190001 −3.537677000 −0.920639000 −2.7981540001 −7.502806000 −0.295766000 −0.6824960001 −5.980139000 2.354937000 2.9487170001 −6.749668000 2.067505000 1.3675010001 −5.195544000 2.949245000 1.463445000

Zero-point correction = 0.406205 (Hartree/Particle)Thermal correction to energy = 0.435958Thermal correction to enthalpy = 0.436903Thermal correction to Gibbs free energy = 0.341428Sum of electronic and zero-point energies = −1453.354099Sum of electronic and thermal energies = −1453.324345Sum of electronic and thermal enthalpies = −1453.323401Sum of electronic and thermal free energies = −1453.418876

d. cis Isomers-2b

Detailed 1H and 13C NMR Spectral Data Assignment for Two Dihydrobenzofuran Neolignans J. Braz. Chem. Soc.S22

6 −3.097406000 0.179835000 0.2204420006 −2.875286000 −1.205647000 0.2895280006 −1.616385000 −1.749903000 0.5031860006 −0.550965000 −0.855263000 0.6590710006 −0.741951000 0.515785000 0.5671100006 −1.998353000 1.045260000 0.3509630008 0.738013000 −1.209796000 0.9186270006 1.446576000 −0.003615000 1.3216040006 0.603776000 1.187517000 0.7252010006 1.133327000 1.693735000 −0.6219890008 0.912680000 1.123416000 −1.6551110008 1.888560000 2.817028000 −0.6512190006 2.217556000 3.562374000 0.5281160008 −1.504999000 −3.104561000 0.6300550006 −0.483210000 −3.752742000 −0.1424670006 −4.415753000 0.762510000 0.0147140006 −5.588352000 0.126310000 −0.1397450006 −6.824233000 0.915823000 −0.3278820008 −7.998907000 0.247773000 −0.5106900006 −8.060351000 −1.179587000 −0.5547800008 −6.860613000 2.122771000 −0.3262780006 2.903597000 −0.111609000 0.9709870006 3.323028000 −0.580999000 −0.2759690006 4.668672000 −0.664049000 −0.5987910006 5.632503000 −0.270678000 0.3452370006 5.220822000 0.196728000 1.5881230006 3.867784000 0.266823000 1.9014770008 6.947445000 −0.387686000 −0.0032510008 5.034656000 −1.201206000 −1.8033990006 5.579390000 −0.277689000 −2.7563080001 −3.695997000 −1.904178000 0.189362000

1 −2.148886000 2.116130000 0.2788580001 1.347640000 0.061767000 2.4094620001 0.572658000 1.991797000 1.4567490001 2.877765000 4.356812000 0.1878020001 2.746325000 2.945361000 1.2552090001 1.327865000 4.008134000 0.9773830001 −0.631092000 −4.819464000 0.0128560001 0.513237000 −3.463829000 0.1904930001 −0.602619000 −3.517387000 −1.2035720001 −4.453859000 1.847701000 −0.0156990001 −5.642137000 −0.952490000 −0.1263960001 −9.106881000 −1.418291000 −0.7318710001 −7.749575000 −1.624898000 0.3928570001 −7.459917000 −1.582315000 −1.3731850001 2.603382000 −0.897478000 −1.0189100001 5.964920000 0.483058000 2.3248600001 3.569958000 0.605377000 2.8878070001 7.502551000 −0.115721000 0.7365600001 5.803776000 −0.863460000 −3.6456080001 6.494441000 0.183163000 −2.3802040001 4.843061000 0.492790000 −3.001653000

Zero-point correction = 0.406399 (Hartree/Particle)Thermal correction to energy = 0.436047Thermal correction to enthalpy = 0.436992Thermal correction to Gibbs free energy = 0.342217Sum of electronic and zero-point energies = −1453.354768Sum of electronic and thermal energies = −1453.325119Sum of electronic and thermal enthalpies = −1453.324175Sum of electronic and thermal free energies = −1453.418949