Hydrazone Radical Promoted Vicinal Difunctionalization of Alkenes and Trifunctionalization of Allyls: Synthesis of Pyrazolines and Tetrahydropyridazines
Xiao-Yong Duan; Xiu-Long Yang; Ran Fang; Xie-Xue Peng; Wei Yu; Bing Han; Journal of Organic Chemistry 78 (2013) 10692–10704; doi:10.1021/jo4016908

data_4028701
_publ_contact_author_name
;
;
_publ_section_title
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 Hydrazone Radical Promoted Vicinal Difunctionalization of Alkenes and
 Trifunctionalization of Allyls: Synthesis of Pyrazolines and
 Tetrahydropyridazines
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_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              10692
_journal_page_last               10704
_journal_paper_doi               10.1021/jo4016908
_journal_volume                  78
_journal_year                    2013
_chemical_formula_moiety         'C39 H59 N4 O2'
_chemical_formula_sum            'C39 H59 N4 O2'
_chemical_formula_weight         615.90
_chemical_name_systematic
;
 ? 
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yab'
_space_group_name_H-M_alt        'P 1 21/a 1'
_symmetry_space_group_name_Hall  '-P 2yab'
_symmetry_space_group_name_H-M   'P 1 21/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2012-11-23
_audit_creation_method
;
  Olex2 1.2
  (compiled Nov  5 2012 18:22:26, GUI svn.r4372)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 113.234(7)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   10.7783(6)
_cell_length_b                   31.1615(16)
_cell_length_c                   11.9415(7)
_cell_measurement_reflns_used    2906
_cell_measurement_temperature    121.16(10)
_cell_measurement_theta_max      28.5113
_cell_measurement_theta_min      2.9112
_cell_volume                     3685.5(4)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
'SUPERFLIP, J. Appl. Cryst. (2007) 40, 786-790'
_diffrn_ambient_temperature      121.16(10)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.9978
_diffrn_measured_fraction_theta_max 0.9792
_diffrn_measurement_details
;
  1 omega  -13.00   22.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.3492  -99.0000   60.0000 35

  2 omega   24.00   92.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6305   57.0000   30.0000 68

  3 omega  -53.00  -28.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6305  -19.0000 -150.0000 25

  4 omega  -22.00   72.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6305  -19.0000 -150.0000 94

  5 omega   65.00  102.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6305  178.0000    0.0000 37
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0325139000
_diffrn_orient_matrix_UB_12      0.0152259000
_diffrn_orient_matrix_UB_13      -0.0234380000
_diffrn_orient_matrix_UB_21      0.0361896000
_diffrn_orient_matrix_UB_22      -0.0167870000
_diffrn_orient_matrix_UB_23      -0.0136621000
_diffrn_orient_matrix_UB_31      -0.0525341000
_diffrn_orient_matrix_UB_32      -0.0021739000
_diffrn_orient_matrix_UB_33      -0.0586686000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0384
_diffrn_reflns_av_unetI/netI     0.0637
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       41
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            17277
_diffrn_reflns_theta_full        28.57
_diffrn_reflns_theta_max         28.57
_diffrn_reflns_theta_min         2.92
_diffrn_source                   'SuperNova (Mo) x-ray Source'
_exptl_absorpt_coefficient_mu    0.068
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92299
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour
;
;
_exptl_crystal_density_diffrn    1.110
_exptl_crystal_description
;
;
_exptl_crystal_F_000             1348
_refine_diff_density_max         0.159
_refine_diff_density_min         -0.184
_refine_diff_density_rms         0.037
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     441
_refine_ls_number_reflns         8349
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.1414
_refine_ls_R_factor_gt           0.0747
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0424P)^2^+2.3126P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1524
_refine_ls_wR_factor_ref         0.1875
_reflns_number_gt                4427
_reflns_number_total             8349
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo4016908_si_003.cif
_cod_data_source_block           yangxiul1222
_cod_database_code               4028701
_reflns_odcompleteness_completeness 99.78
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  H5 of C5, H4 of C4, H3 of C3, H2 of C2, H1 of C1, {H34A,H34B} of C34, {H35A,
  H35B} of C35, {H36A,H36B} of C36, {H24A,H24B} of C24, {H23A,H23B} of C23,
  {H21A,H21B} of C21, H20 of C20, H19 of C19, H18 of C18, H17 of C17, H16 of
  C16, H15 of C15, {H25A,H25B} of C25, H9 of C9, {H11A,H11B} of C11A, {H11C,
  H11D} of C11B, {H12A,H12B} of C12A, {H12C,H12D} of C12B
 At 1.5 times of:
  {H32A,H32B,H32C} of C32, {H33A,H33B,H33C} of C33, {H38A,H38B,H38C} of C38,
  {H39A,H39B,H39C} of C39, {H26A,H26B,H26C} of C26, {H28A,H28B,H28C} of C28,
  {H29A,H29B,H29C} of C29, {H30A,H30B,H30C} of C30, {H10A,H10B,H10C} of C10
2. Restrained distances
 H13B-C13
 0.94 with sigma of 0.01
 H13A-C13
 0.94 with sigma of 0.01
3. others
 Fixed Sof: C11A(0.4) H11A(0.4) H11B(0.4) C11B(0.6) H11C(0.6) H11D(0.6)
 C12A(0.4) H12A(0.4) H12B(0.4) C12B(0.6) H12C(0.6) H12D(0.6)
4.a Ternary CH refined with riding coordinates:
 C9(H9), C20(H20)
4.b Secondary CH2 refined with riding coordinates:
 C11A(H11A,H11B), C11B(H11C,H11D), C12A(H12A,H12B), C12B(H12C,H12D), C21(H21A,
 H21B), C23(H23A,H23B), C24(H24A,H24B), C25(H25A,H25B), C34(H34A,H34B),
 C35(H35A,H35B), C36(H36A,H36B)
4.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C15(H15), C16(H16), C17(H17),
 C18(H18), C19(H19)
4.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,
 H29C), C30(H30A,H30B,H30C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C38(H38A,
 H38B,H38C), C39(H39A,H39B,H39C)
;