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_4027549
_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         'C22 H23 F2 N O4'
_chemical_formula_sum            'C22 H23 F2 N O4'
_chemical_formula_weight         403.425
_space_group_IT_number           19
_symmetry_cell_setting           orthorhombic
_symmetry_Int_Tables_number      19
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   6.13970(10)
_cell_length_b                   10.0767(3)
_cell_length_c                   31.8096(11)
_cell_measurement_reflns_used    2224
_cell_measurement_temperature    298
_cell_measurement_theta_max      27.485
_cell_measurement_theta_min      0.998
_cell_volume                     1967.99(10)
_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 0.981
_diffrn_measured_fraction_theta_max 0.981
_diffrn_measurement_device       KappaCCD
_diffrn_measurement_method       CCD
_diffrn_orient_matrix_type       X=UH
_diffrn_orient_matrix_UB_11      0.05003
_diffrn_orient_matrix_UB_12      -0.09497
_diffrn_orient_matrix_UB_13      0.12250
_diffrn_orient_matrix_UB_21      -0.07685
_diffrn_orient_matrix_UB_22      -0.06078
_diffrn_orient_matrix_UB_23      -0.01573
_diffrn_orient_matrix_UB_31      0.01739
_diffrn_orient_matrix_UB_32      -0.01678
_diffrn_orient_matrix_UB_33      -0.02011
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           ' MoK\a'
_diffrn_radiation_wavelength_id  all
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            8496
_diffrn_reflns_theta_full        27.50
_diffrn_reflns_theta_max         27.50
_diffrn_reflns_theta_min         1.28
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    0.106
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            Colourless
_exptl_crystal_density_diffrn    1.362
_exptl_crystal_description       Prism
_exptl_crystal_F_000             848
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.10
_refine_diff_density_max         0.459
_refine_diff_density_min         -0.206
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.3(10)
_refine_ls_extinction_coef       0.048(9)
_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   1.049
_refine_ls_hydrogen_treatment    refxyz
_refine_ls_matrix_type           full
_refine_ls_number_parameters     263
_refine_ls_number_reflns         4359
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0682
_refine_ls_R_factor_gt           0.0530
_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^)+(0.0712P)^2^+0.5996P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1297
_refine_ls_wR_factor_ref         0.1410
_reflns_number_gt                3626
_reflns_number_total             4359
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo301327s_si_001_3.cif
_cod_data_source_block           19cis
_cod_database_code               4027549