Stereoselective synthesis of hydrazinodihydrofurans via cascade Michael addition-substitution involving the reaction of curcumin and other β-dicarbonyls with α-hydrazinonitroalkenes.
Bera, Kalisankar; Ayyagari, Narasimham; Satam, Nishikant; Namboothiri, Irishi N. N.; Organic & biomolecular chemistry 18 (2019) 140–153; doi:10.1039/c9ob01974j

data_7157231
_publ_section_title
;
 Stereoselective synthesis of hydrazinodihydrofurans via cascade Michael
 addition-substitution involving the reaction of curcumin and other
 \b-dicarbonyls with \a-hydrazinonitroalkenes.
;
_journal_issue                   1
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              140
_journal_page_last               153
_journal_paper_doi               10.1039/c9ob01974j
_journal_volume                  18
_journal_year                    2019
_chemical_absolute_configuration 0.02
_chemical_formula_moiety         'C25 H34 N2 O7, C25 H33 N O8'
_chemical_formula_sum            'C50 H67 N3 O15'
_chemical_formula_weight         950.06
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-06-02
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2015.10.28 svn.r3245 for OlexSys, GUI svn.r5128)
;
_audit_update_record
;
2019-08-26 deposited with the CCDC.	2019-11-26 downloaded from the CCDC.
;
_cell_angle_alpha                91.460(2)
_cell_angle_beta                 98.011(2)
_cell_angle_gamma                104.143(2)
_cell_formula_units_Z            1
_cell_length_a                   10.4124(3)
_cell_length_b                   11.3067(3)
_cell_length_c                   11.3573(3)
_cell_measurement_reflns_used    27030
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      72.7280
_cell_measurement_theta_min      3.9140
_cell_volume                     1281.44(6)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -191.00 -38.00   1.00    6.00    -- -101.00   0.00  36.00  153
  2  \w   -122.00  58.00   1.00    6.00    --  -32.00   0.00 108.00  180
  3  \w   -135.00 -29.00   1.00    6.00    -- -101.00  72.00-108.00  106
  4  \w   -106.00 -11.00   1.00    6.00    -- -101.00  72.00   0.00   95
  5  \w   -107.00 -17.00   1.00    6.00    -- -101.00  72.00 108.00   90
  6  \w   -191.00-101.00   1.00    6.00    -- -101.00 -44.00-180.00   90
  7  \w   -191.00 -80.00   1.00    6.00    -- -101.00 -72.00 -72.00  111
  8  \w    -66.00 -13.00   1.00    6.00    --  -32.00  72.00-144.00   53
  9  \w   -106.00 -11.00   1.00    6.00    -- -101.00  72.00-144.00   95
 10  \w    -66.00 -19.00   1.00    6.00    --  -32.00  72.00  36.00   47
 11  \w    -97.00 -22.00   1.00    6.00    -- -101.00  72.00 144.00   75
 12  \w   -106.00 -76.00   1.00    6.00    -- -101.00  72.00 -36.00   30
 13  \w    -94.00 -38.00   1.00    6.00    -- -101.00  72.00  36.00   56
 14  \w   -100.00 -41.00   1.00    6.00    -- -101.00  72.00-180.00   59
 15  \w   -122.00 -92.00   1.00    6.00    --  -32.00 -15.00 108.00   30
 16  \w   -100.00 -23.00   1.00    6.00    -- -101.00  72.00  72.00   77
 17  \w    -98.00 -68.00   1.00    6.00    -- -101.00  72.00 -72.00   30
 18  \w    -64.00 -34.00   1.00    6.00    --  -32.00 -72.00 -36.00   30
 19  \w   -191.00 -67.00   1.00    6.00    -- -101.00 -72.00  72.00  124
 20  \w   -191.00 -67.00   1.00    6.00    -- -101.00 -72.00 144.00  124
 21  \w   -191.00 -67.00   1.00    6.00    -- -101.00 -72.00   0.00  124
 22  \w   -122.00   2.00   1.00    6.00    --  -32.00   0.00-180.00  124
 23  \w   -191.00 -68.00   1.00    6.00    -- -101.00 -72.00-108.00  123
 24  \w    -66.00  22.00   1.00    6.00    --  -32.00  72.00   0.00   88
 25  \w   -191.00 -67.00   1.00    6.00    -- -101.00 -72.00 -36.00  124
 26  \w   -191.00 -67.00   1.00    6.00    -- -101.00 -72.00-180.00  124
 27  \w    -61.00 -12.00   1.00    6.00    --  -32.00  72.00-180.00   49
 28  \w   -191.00 -67.00   1.00    6.00    -- -101.00 -72.00-144.00  124
 29  \w   -191.00 -67.00   1.00    6.00    -- -101.00 -72.00 108.00  124
 30  \w   -191.00 -67.00   1.00    6.00    -- -101.00 -72.00  36.00  124
 31  \w    -53.00 -10.00   1.00    6.00    --  -32.00 -72.00 144.00   43
 32  \w    -99.00 -68.00   1.00    6.00    -- -101.00  43.00 144.00   31
 33  \w    -30.00   0.00   1.00    6.00    --  -32.00 -72.00   0.00   30
 34  \w    -30.00   0.00   1.00    6.00    --  -32.00 -72.00  72.00   30
 35  \w   -106.00 -76.00   1.00    6.00    -- -101.00  43.00   0.00   30
 36  \w    -36.00  -6.00   1.00    6.00    --  -32.00 -44.00-180.00   30
 37  \w    -97.00 -67.00   1.00    6.00    -- -101.00   0.00-180.00   30
 38  \w    -88.00 -58.00   1.00    6.00    -- -101.00  43.00 108.00   30
 39  \w   -191.00 -11.00   1.00    6.00    -- -101.00   0.00 108.00  180
 40  \w   -122.00  58.00   1.00    6.00    --  -32.00   0.00  36.00  180
 41  \w   -119.00 -34.00   1.00    6.00    -- -101.00  43.00 -36.00   85
 42  \w    -98.00 -32.00   1.00    6.00    -- -101.00  43.00  72.00   66
 43  \w   -127.00 -52.00   1.00    6.00    -- -101.00  43.00-180.00   75
 44  \w    -89.00 -59.00   1.00    6.00    -- -101.00  43.00-108.00   30
 45  \w    -97.00 -57.00   1.00    6.00    -- -101.00  43.00-144.00   40
 46  \w   -107.00 -55.00   1.00    6.00    -- -101.00  43.00  36.00   52
 47  \w    -30.00   2.00   1.00    6.00    --  -32.00 -72.00-144.00   32
 48  \w    -60.00 -29.00   1.00    6.00    --  -32.00  72.00 108.00   31
 49  \w    -97.00 -36.00   1.00    6.00    -- -101.00  43.00 -72.00   61
 50  \w    -56.00 -21.00   1.00    6.00    --  -32.00 -72.00  36.00   35
 51  \w    -49.00 -18.00   1.00    6.00    --  -32.00 -72.00-180.00   31
 52  \w    -32.00  -2.00   1.00    6.00    --  -32.00 -72.00 -72.00   30
 53  \w    -47.00 -14.00   1.00    6.00    --  -32.00 -72.00 108.00   33
 54  \w    -53.00 -23.00   1.00    6.00    --  -32.00  72.00-108.00   30
 55  \w   -191.00-159.00   1.00    6.00    -- -101.00 -44.00 -72.00   32
 56  \w   -183.00 -78.00   1.00    6.00    -- -101.00 -44.00   0.00  105
 57  \w   -191.00 -75.00   1.00    6.00    -- -101.00 -44.00 -36.00  116
 58  \w   -191.00 -75.00   1.00    6.00    -- -101.00 -44.00-108.00  116
 59  \w    -66.00  58.00   1.00    6.00    --  -32.00  72.00 -72.00  124
 60  \w   -191.00 -75.00   1.00    6.00    -- -101.00 -44.00  36.00  116
 61  \w    -66.00  15.00   1.00    6.00    --  -32.00  72.00  72.00   81
 62  \w   -191.00 -75.00   1.00    6.00    -- -101.00 -44.00 108.00  116
 63  \w    -60.00  -6.00   1.00    6.00    --  -32.00 -44.00 108.00   54
 64  \w   -191.00 -75.00   1.00    6.00    -- -101.00 -44.00  72.00  116
 65  \w   -191.00 -75.00   1.00    6.00    -- -101.00 -44.00 144.00  116
 66  \w   -191.00 -75.00   1.00    6.00    -- -101.00 -44.00-144.00  116
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0689044000
_diffrn_orient_matrix_UB_12      0.0361245000
_diffrn_orient_matrix_UB_13      0.1019643000
_diffrn_orient_matrix_UB_21      0.1284564000
_diffrn_orient_matrix_UB_22      0.0986915000
_diffrn_orient_matrix_UB_23      0.0487314000
_diffrn_orient_matrix_UB_31      -0.0506830000
_diffrn_orient_matrix_UB_32      0.0936728000
_diffrn_orient_matrix_UB_33      -0.0778773000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1134
_diffrn_reflns_av_unetI/netI     0.0615
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            43857
_diffrn_reflns_point_group_measured_fraction_full 0.907
_diffrn_reflns_point_group_measured_fraction_max 0.907
_diffrn_reflns_theta_full        64.995
_diffrn_reflns_theta_max         64.995
_diffrn_reflns_theta_min         3.938
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.751
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66265
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.231
_exptl_crystal_description       plate
_exptl_crystal_F_000             508
_exptl_crystal_size_max          0.197
_exptl_crystal_size_mid          0.061
_exptl_crystal_size_min          0.044
_refine_diff_density_max         0.646
_refine_diff_density_min         -0.475
_refine_diff_density_rms         0.138
_refine_ls_abs_structure_details
;
 Flack x determined using 3030 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.0(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     627
_refine_ls_number_reflns         7928
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.078
_refine_ls_R_factor_all          0.0721
_refine_ls_R_factor_gt           0.0626
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1282P)^2^+0.2308P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1638
_refine_ls_wR_factor_ref         0.1793
_reflns_Friedel_coverage         0.838
_reflns_Friedel_fraction_full    0.827
_reflns_Friedel_fraction_max     0.827
_reflns_number_gt                7474
_reflns_number_total             7928
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ob01974j2.cif
_cod_data_source_block           inn-ksb-dmq-ome-a_cu
_cod_depositor_comments          'Adding full bibliography for 7157231.cif.'
_cod_original_cell_volume        1281.45(6)
_cod_database_code               7157231
_chemical_oxdiff_formula         C25H34N2O7
_reflns_odcompleteness_completeness 97.37
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     72.69
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C00S(H00S), C017(H017), C019(H019), C01C(H1AA), C01D(H2AA), C01I(H01I),
 C01J(H01J), C01T(H8AA)
2.b Secondary CH2 refined with riding coordinates:
 C00Q(H00A,H00B), C010(H01,H), C014(H01A,H01B), C01O(H4AA,HE)
2.c Aromatic/amide H refined with riding coordinates:
 N00H(H00H), C00O(H00O), C011(H011), C012(H012), C016(H016), C018(H018),
 C01A(H01C), C01E(H01E), C01P(H01V)
2.d Idealised Me refined as rotating group:
 C00W(H00C,H00D,H00E), C01B(H0AA,HA,HB), C01F(H01D,H01F,H01G), C01H(H3AA,HC,
 HD), C01K(H01H,H01K,H01L), C01L(H01M,H01N,H01O), C01M(H01P,H01Q,H01R),
 C01N(H01S,H01T,H01U), C01Q(H5AA,HF,HG), C01R(H6AA,HH,HI), C01S(H7AA,HJ,HK),
 C01U(H01W,H01X,H01Y), C01V(H01Z,HL,HM), C01W(H9AA,HN,HO)
;
_shelx_res_checksum              25158
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 4.651
_oxdiff_exptl_absorpt_empirical_full_min 0.425