Sterically Biased 3,3-Sigmatropic Rearrangement of Chiral Allylic Azides: Application to the Total Syntheses of Alkaloids
Sophie Lauzon; François Tremblay; David Gagnon; Cédrickx Godbout; Christine Chabot; Catherine Mercier-Shanks; Stéphane Perreault; Hélène DeSève; Claude Spino; Journal of Organic Chemistry 73 (2008) 6239–6250; doi:10.1021/jo800817p

data_4023600
_publ_section_title
;
 Sterically Biased 3,3-Sigmatropic Rearrangement of Chiral Allylic
 Azides: Application to the Total Syntheses of Alkaloids
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              6239
_journal_page_last               6250
_journal_paper_doi               10.1021/jo800817p
_journal_volume                  73
_journal_year                    2008
_chemical_absolute_configuration ad
_chemical_formula_sum            'C26 H36 F3 N O2'
_chemical_formula_weight         451.56
_space_group_IT_number           4
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_conform_dict_location     ftp://ftp.iucr.org/pub/cif_core.dic
_audit_conform_dict_name         cif_core.dic
_audit_conform_dict_version      2.3
_audit_creation_date             2006-08-07T11:29:27-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_cell_angle_alpha                90
_cell_angle_beta                 98.86(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.849(4)
_cell_length_b                   9.768(9)
_cell_length_c                   17.364(8)
_cell_measurement_reflns_used    20
_cell_measurement_temperature    198(2)
_cell_measurement_theta_max      35
_cell_measurement_theta_min      30
_cell_volume                     1315.4(15)
_computing_cell_refinement       Difrac
_computing_data_collection       Difrac
_computing_data_reduction        NRCVAX
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_diffrn_ambient_temperature      198(2)
_diffrn_measured_fraction_theta_full 0.981
_diffrn_measured_fraction_theta_max 0.981
_diffrn_measurement_device_type  CAD4
_diffrn_measurement_method       Omega
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54176
_diffrn_reflns_av_R_equivalents  0
_diffrn_reflns_av_unetI/netI     0.0296
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            2621
_diffrn_reflns_theta_full        70.38
_diffrn_reflns_theta_max         70.38
_diffrn_reflns_theta_min         2.58
_diffrn_standards_decay_%        0
_diffrn_standards_interval_count 100
_diffrn_standards_number         1
_exptl_absorpt_coefficient_mu    0.705
_exptl_absorpt_correction_T_max  0.6478
_exptl_absorpt_correction_T_min  0.5869
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details   'psi scan'
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.14
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       Needle
_exptl_crystal_F_000             484
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.268
_refine_diff_density_min         -0.299
_refine_diff_density_rms         0.061
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.1(10)
_refine_ls_extinction_coef       0.0045(10)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.15
_refine_ls_hydrogen_treatment    none
_refine_ls_matrix_type           full
_refine_ls_number_parameters     300
_refine_ls_number_reflns         2621
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.15
_refine_ls_R_factor_all          0.0865
_refine_ls_R_factor_gt           0.072
_refine_ls_shift/su_max          0
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0928P)^2^+1.2881P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1949
_refine_ls_wR_factor_ref         0.2087
_reflns_number_gt                2181
_reflns_number_total             2621
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo800817p-file004.cif
_cod_data_source_block           ems1118fb
_cod_depositor_comments
;
The following automatic conversions were performed:
'_symmetry_cell_setting' value 'Monoclinic' changed to 'monoclinic'
according to '/home/saulius/struct/CIF-dictionaries/cif_core.dic'
dictionary named 'cif_core.dic' version 2.4.1 from
2010-06-29.

'_exptl_absorpt_correction_type' value 'Empirical' changed to
'empirical' according to
'/home/saulius/struct/CIF-dictionaries/cif_core.dic' dictionary named
'cif_core.dic' version 2.4.1 from 2010-06-29.

Automatic conversion script
Id: cif_fix_enum 1527 2010-12-29 10:47:43Z saulius 
;
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               4023600