Detailed <sup>1</sup>H and <sup>13</sup>C NMR Spectral Data Assignment for Two Dihydrobenzofuran Neolignans

Talita C. T. Medeiros

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

# These authors contributed equally to this work.

Herbert J. Dias

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

# These authors contributed equally to this work.

Eliane O. Silva

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

Murilo J. Fukui

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

Ana Carolina F. Soares

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

Tapas Kar

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

Vladimir C. G. Heleno

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

Paulo M. Donate

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

Renato L. T. Parreira

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

Antônio E. M. Crotti ^**e-mail: millercrotti@ffclrp.usp.br

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

	δ_C^a a Multiplicities assigned on the basis of distortionless enhancement by polarization transfer (DEPT) 135 experiments;	δ_H (integral, multiplicity^b b multiplicities and coupling constant values measured within 1H NMR and J-resolved spectra with the help from 1H-1H correlation spectroscopy (COSY) results. ), J/ Hz
1	132.0 (C)	−
2=6	127.5 (CH)	7.27 (2H, ddd, J_2,5 = J_6,3 0.3, J_2,7 = J_6,7 0.6, J_2,3 = J_6,5 8.3)
3=5	115.7 (CH)	6.84 (2H, dd, J_3,6 = J_5,2 0.3, J_3,2 = J_5,6 8.3)
4	156.1 (C)	−
7	87.7 (CH)	6.09 (1H, dt, J_7,2 = J_7,6 0.6, J_7,8 7.2)
8	55.1 (CH)	4.27 (1H, dd, J_8,6' 1.4, J_8,7 7.2)
9	170.9 (C)	−
10	52.9 (CH₃)	3.83 (3H, s)
1'	127.8 (C)	−
2'	130.8 (CH)	7.43 (1H, ddd, J_2',7' 1.1, J_2',6' 2.0, J_2',3' 8.3)
3'	110.3 (CH)	6.89 (1H, dd, J_3',6' 0.4, J_3',2'8.3)
4'	161.2 (C)	−
5'	125.1 (C)	−
6'	124.9 (CH)	7.55 (1H, dddd, J_6',3' 0.4, J_6',7' 0.7, J_6',8 1.4, J_6',2'2.0)
7'	144.7 (CH)	7.66 (1H, ddd, J_7',6' 0.7, J_7',2' 1.1, J_7',8' 15.9)
8'	115.2 (CH)	6.32 (1H, d, J_8',7' 15.9)
9'	167.9 (C)	−
10'	51.7 (CH₃)	3.81 (3H, s)

C	H	gCOSY^a a Gradient-selected correlation spectroscopy;	gHMBC^b b gradient-selected heteronuclear multiple bond coherence;	gHMQC^c c gradient-selected heteronuclear multiple quantum coherence;	NOESY^d d nuclear Overhauser effect spectroscopy.
1	–	–	H₃ =H₅, H₇, H₈	–	–
2=6	2=6	H₃, H₅, H₇	H₃ =H₅, H₇	H₂=H₆	H₇, H₈
3=5	3=5	H₂, H₆	H₅	H₃=H₅	–
4	–	–	H₃ =H₅, H₂ =H₆	–	–
7	7	H₂=H₆, H₈	H₆, H₈	H₇	H₂=H₆^* * mean weak correlation.
8	8	H₇, H_6'	H₇, H_6'	H₈	H₂=H₆, H_6'^* * mean weak correlation.
9	–	–	H₇, H₈, H₁₀	–	–
10	10	–	−	H₁₀	–
1'	–	–	H_3', H_8'	–	–
2'	2'	H_3', H_6', H_7'	H_6', H_7'	H_2'	H_7', H_8'^* * mean weak correlation.
3'	3'	H_2', H_6'	−	H_3'	–
4'	–	–	H_2', H_3', H_6', H₇, H₈	–	–
5'	–	–	H₈, H_3'	–	–
6'	6'	H_2', H_3', H_7', H₈	H_2', H_7', H₈	H_6'	H_8', H_7', H₈^* * mean weak correlation.
7'	7'	H_2', H_8', H_6'	H_2', H_6', H_8'	H_7'	H_6'^* * mean weak correlation. , H_2'
8'	8'	_H7'	H_7'	H_8'	H_6'^* * mean weak correlation. , H_2'
9'	–	–	H_7', H_8', H_10'	–	–
10'	10'	–	–	H_10'	–

	δ_C^a a Multiplicities assigned on the basis of distortionless enhancement by polarization transfer (DEPT) 135 experiments;	δ_H (integral, multiplicity^b b multiplicities and coupling constant values measured within 1H-NMR and J-resolved spectra with the help from 1H-1H correlation spectroscopy (COSY) results. ); J/ Hz
1	132.5 (C)	–
2	111.2 (CH)	7.10 (1H, ddd, J_2,5 0.3, J_2,7 0.8, J_2,6 2.1)
3	149.1 (C)	–
4	148.5 (C)	–
5	116.3 (CH)	6.84 (1H, dd, J_5,2 0.3, J_5,6 8.3)
6	120.7 (CH)	6.92 (1H, ddd, J_6,7 0.6, J_6,2 2.1, J_6,5 8.3)
7	88.8 (CH)	6.04 (1H, ddd, J_7,6 0.6, J_7,2 0.8, J_7,8 7.3)
8	57.0 (CH)	4.47 (1H, dd, J_8,6' 1.4, J_8,7 7.3)
9	172.1 (C=O)	–
10	53.5 (CH₃)	3.81 (3H, s)
11	56.4 (CH₃)	3.84 (3H, s)
1'	129.9 (C)	–
2'	113.9 (CH)	7.33 (1H, dd, J_2',7' 0.4, J_2'6' 2.6)
3'	146.3 (C)	–
4'	151.5 (C)	–
5'	127.8 (C)	–
6'	119.5 (CH)	7.29 (1H, ddd, J_6',7' 0.8, J_6',8 1.4, J_6',2' 2.6)
7'	145.9 (CH)	7.63 (1H, ddd, J_7',2' 0.4, J_7',6' 0.8, J_7',8' 15.8)
8'	116.8 (CH)	6.44 (1H, d, J_8',7' 15.8)
9'	168.2 (C)	–
10'	52.1 (CH₃)	3.73 (3H, s)
11'	56.8 (CH₃)	3.92 (3H, s)

C	H	gCOSY^a a Gradient-selected correlation spectroscopy;	gHMBC^b b gradient-selected heteronuclear multiple bond coherence;	gHMQC^c c gradient-selected heteronuclear multiple quantum coherence;	NOESY^d d nuclear Overhauser effect spectroscopy.
1	–	–	H₂, H₆, H₇, H₈	–	–
2	2	H₅, H₆, H₇	H₅, H₆, H₇	H₂	H₇, H₈, H₁₁
3	–	–	H₂, H₅, H₁₁	H₃	–
4	–	–	H₂, H₅, H₆	–	–
5	5	H₂, H₆	H₆	H₅	–
6	6	H₂, H₅, H₇	H₂, H₅	H₆	H₇, H₈
7	7	H₂, H₆, H₈	H₂, H₆, H₈	H₇	H₆^* * mean weak correlation. , H₂
8	8	H_6', H₇	H₂, H_6'	H₈	H_6'^* * mean weak correlation. , H₂, H₆
9	–	–	H₇, H₈, H₁₀	H₉	–
10	10	–	−	H₁₀	–
11	11	–	−	H₁₁	H₂
1'	–	–	H_7', H_8'	H_1'	–
2'	2'	H_6', H_7'	H_6', H_7'	H_2'	H_7', H_8'^* * mean weak correlation. , H_11'
3'	–	–	H_11'	–	–
4'	–	–	H_2', H_6', H₇, H₈	–	–
5'	–	–	H₇, H_8'	–	–
6'	6'	H_7', H_2', H₈	H_2', H_7', H₈	H_6'	H_8', H_7', H₈^* * mean weak correlation.
7'	7'	H_2', H_6', H_8'	H_2', H_6', H_8'	H_7'	H_6', H_2',
8'	8'	H_7'	H_7'	H_8'	H_6', H_2'
9'	–	–	H_8', H_10'	–	–
10'	10'	–	–	H_10'	–
11'	11'	–	–	H_11'	H_2'

	Compound 2a^a a Calculated in CDCl3;		Compound 2b^b b calculated in acetone-d6.
	trans	cis	trans	cis
Only δ_H	0.46	0.49	0.39	0.42
Only δ_C	6.52	6.91	7.32	7.92
δ_H + δ_C	5.09	5.39	5.81	6.29

Brasil