Asymmetric Synthesis of gem-Difluoromethylenated Dihydroxypyrrolizidines and Indolizidines
Watcharaporn Thaharn; Teerawut Bootwicha; Darunee Soorukram; Chutima Kuhakarn; Samran Prabpai; Palangpon Kongsaeree; Patoomratana Tuchinda; Vichai Reutrakul; Manat Pohmakotr; Journal of Organic Chemistry 77 (2012) 8465–8479; doi:10.1021/jo301327s

data_4027551
_publ_contact_author_address
;Department of Chemistry, Faculty of Science
Mahidol University
Rama VI, Bangkok 10400, Thailand
;
_publ_contact_author_email       palangpon@gmail.com
_publ_contact_author_fax         +662-354-7151
_publ_contact_author_name        ' Palangpon Kongsaeree'
_publ_contact_author_phone       ' +662-201-5190'
_publ_section_title
;
 Asymmetric Synthesis of gem-Difluoromethylenated Dihydroxypyrrolizidines
 and Indolizidines
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              8465
_journal_page_last               8479
_journal_paper_doi               10.1021/jo301327s
_journal_volume                  77
_journal_year                    2012
_chemical_absolute_configuration unk
_chemical_compound_source        Synthesis
_chemical_formula_moiety         'C23 H25 F2 N O4 '
_chemical_formula_sum            'C23 H25 F2 N O4'
_chemical_formula_weight         417.452
_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
_cell_angle_alpha                90.00
_cell_angle_beta                 114.293(4)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   11.898(2)
_cell_length_b                   8.1310(6)
_cell_length_c                   12.412(2)
_cell_measurement_reflns_used    1595
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      25.028
_cell_measurement_theta_min      0.998
_cell_volume                     1094.4(3)
_computing_cell_refinement       'HKL Scalepack (Otwinowski & Minor 1997)'
_computing_data_collection       KappaCCD
_computing_data_reduction        'Denzo and Scalepak (Otwinowski & Minor, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution
'SIR97(Cascarano al.,Acta Cryst.,1996,A52,C-79)'
_diffrn_ambient_temperature      298(2)
_diffrn_measured_fraction_theta_full 0.964
_diffrn_measured_fraction_theta_max 0.964
_diffrn_measurement_device       KappaCCD
_diffrn_measurement_method       CCD
_diffrn_orient_matrix_type       X=UH
_diffrn_orient_matrix_UB_11      -0.02678
_diffrn_orient_matrix_UB_12      -0.07315
_diffrn_orient_matrix_UB_13      -0.04934
_diffrn_orient_matrix_UB_21      -0.11330
_diffrn_orient_matrix_UB_22      0.04711
_diffrn_orient_matrix_UB_23      -0.00835
_diffrn_orient_matrix_UB_31      0.01029
_diffrn_orient_matrix_UB_32      0.00928
_diffrn_orient_matrix_UB_33      -0.08730
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           ' MoK\a'
_diffrn_radiation_wavelength_id  all
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            4898
_diffrn_reflns_theta_full        25.16
_diffrn_reflns_theta_max         25.16
_diffrn_reflns_theta_min         1.80
_exptl_absorpt_coefficient_mu    0.097
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            Colourless
_exptl_crystal_density_diffrn    1.267
_exptl_crystal_description       Plate
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.10
_refine_diff_density_max         0.186
_refine_diff_density_min         -0.157
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.3(13)
_refine_ls_extinction_coef       0.096(17)
_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   1.033
_refine_ls_hydrogen_treatment    refxyz
_refine_ls_matrix_type           full
_refine_ls_number_parameters     272
_refine_ls_number_reflns         3388
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0970
_refine_ls_R_factor_gt           0.0553
_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^)+(0.0667P)^2^+0.3099P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1265
_refine_ls_wR_factor_ref         0.1508
_reflns_number_gt                2255
_reflns_number_total             3388
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo301327s_si_001_5.cif
_cod_data_source_block           13-cis
_cod_original_cell_volume        1094.5(2)
_cod_original_sg_symbol_H-M      'P 21 '
_cod_original_formula_sum        'C23 H25 F2 N O4 '
_cod_database_code               4027551