Amine-Catalyzed Asymmetric (3 + 3) Annulations of β'-Acetoxy Allenoates: Enantioselective Synthesis of 4H-Pyrans.
Ni, Chunjie; Tong, Xiaofeng; Journal of the American Chemical Society 138 (2016) 7872–7875; doi:10.1021/jacs.6b04935

data_4130587
_publ_section_title
;
 Amine-Catalyzed Asymmetric (3 + 3) Annulations of \b'-Acetoxy Allenoates:
 Enantioselective Synthesis of 4H-Pyrans.
;
_journal_issue                   25
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              7872
_journal_page_last               7875
_journal_paper_doi               10.1021/jacs.6b04935
_journal_volume                  138
_journal_year                    2016
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C22 H19 Br N2 O3'
_chemical_formula_sum            'C22 H19 Br N2 O3'
_chemical_formula_weight         439.30
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-11-10
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_cell_angle_alpha                90
_cell_angle_beta                 104.347(5)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   14.7436(11)
_cell_length_b                   20.1400(12)
_cell_length_c                   27.3915(19)
_cell_measurement_reflns_used    5132
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      64.480
_cell_measurement_theta_min      3.794
_cell_volume                     7879.9(9)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.981
_diffrn_measured_fraction_theta_max 0.953
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0875
_diffrn_reflns_av_unetI/netI     0.1192
_diffrn_reflns_Laue_measured_fraction_full 0.981
_diffrn_reflns_Laue_measured_fraction_max 0.953
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            33240
_diffrn_reflns_point_group_measured_fraction_full 0.919
_diffrn_reflns_point_group_measured_fraction_max 0.886
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         69.783
_diffrn_reflns_theta_min         3.794
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.056
_exptl_absorpt_correction_T_max  0.7532
_exptl_absorpt_correction_T_min  0.4355
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1473 before and 0.0885 after correction.
The Ratio of minimum to maximum transmission is 0.5782.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.481
_exptl_crystal_description       block
_exptl_crystal_F_000             3584
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.867
_refine_diff_density_min         -0.919
_refine_diff_density_rms         0.109
_refine_ls_abs_structure_details
;
 Flack x determined using 3956 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.037(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1021
_refine_ls_number_reflns         13217
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0872
_refine_ls_R_factor_gt           0.0686
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0915P)^2^+1.8084P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1658
_refine_ls_wR_factor_ref         0.1809
_reflns_Friedel_coverage         0.805
_reflns_Friedel_fraction_full    0.852
_reflns_Friedel_fraction_max     0.815
_reflns_number_gt                10416
_reflns_number_total             13217
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b04935_si_003.cif
_cod_data_source_block           dm15832
_cod_database_code               4130587
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.792
_shelx_estimated_absorpt_t_min   0.657
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C4(H4), C4B(H4B), C4A(H4A), C4C(H4C)
2.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C13(H13), C14(H14), C16(H16), C17(H17), C18(H18),
 C19(H19), C20(H20), C10B(H10B), C11B(H11B), C13B(H13B), C14B(H14B), C16B(H16B),
  C17B(H17B), C18B(H18B), C19B(H19B), C20B(H20B), C10A(H10A), C11A(H11A),
 C13A(H13A), C14A(H14A), C16A(H16A), C17A(H17A), C18A(H18A), C19A(H19A),
 C20A(H20A), C10C(H10C), C11C(H11C), C13C(H13C), C14C(H14C), C16C(H16C),
 C17C(H17C), C18C(H18C), C19C(H19C), C20C(H20C)
2.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C8(H8A,H8B,H8C), C22(H22A,H22B,H22C), C1B(H1BA,H1BB,H1BC),
 C8B(H8BA,H8BB,H8BC), C22B(H22D,H22E,H22F), C1A(H1AA,H1AB,H1AC), C8A(H8AA,H8AB,
 H8AC), C22A(H22G,H22H,H22I), C1C(H1CA,H1CB,H1CC), C8C(H8CA,H8CB,H8CC),
 C22C(H22J,H22K,H22L)
;
_shelx_res_checksum              36738
_shelx_hkl_checksum              24009
_olex2_submission_special_instructions 'No special instructions were received'