Enantioselective Addition of Alkynes to α,α-Dichlorinated Aldehydes.
Sempere Molina, Yeshua; Ruchti, Jonathan; Carreira, Erick M.; Organic letters 19 (2017) 743–745; doi:10.1021/acs.orglett.6b03692

data_1545169
_publ_section_title
;
 Enantioselective Addition of Alkynes to \a,\a-Dichlorinated Aldehydes.
;
_journal_issue                   4
_journal_name_full               'Organic letters'
_journal_page_first              743
_journal_page_last               745
_journal_paper_doi               10.1021/acs.orglett.6b03692
_journal_volume                  19
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C15 H18 Cl2 O2'
_chemical_formula_sum            'C15 H18 Cl2 O2'
_chemical_formula_weight         301.19
_chemical_name_systematic
(-)-R-1-(benzyloxy)-5,5-dichloro-6-methylhept-2-yn-4-ol
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2015-10-15
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.423(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   5.9062(3)
_cell_length_b                   9.1377(4)
_cell_length_c                   13.7532(6)
_cell_measurement_reflns_used    2726
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      27.26
_cell_measurement_theta_min      2.96
_cell_volume                     742.23(6)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 8.33
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_device       'kappa-stage diffractometer'
_diffrn_measurement_device_type  'Bruker/Nonius Kappa Apex2'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0750
_diffrn_reflns_av_unetI/netI     0.0792
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            6284
_diffrn_reflns_point_group_measured_fraction_full 0.912
_diffrn_reflns_point_group_measured_fraction_max 0.892
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.486
_diffrn_reflns_theta_min         2.676
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.432
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6908
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0788 before and 0.0420 after correction.
The Ratio of minimum to maximum transmission is 0.9265.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.348
_exptl_crystal_description       block
_exptl_crystal_F_000             316
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.035
_refine_diff_density_max         0.406
_refine_diff_density_min         -0.303
_refine_diff_density_rms         0.061
_refine_ls_abs_structure_details
;
 Flack x determined using 1033 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.04(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.975
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     177
_refine_ls_number_reflns         3051
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      0.975
_refine_ls_R_factor_all          0.0423
_refine_ls_R_factor_gt           0.0367
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0153P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0668
_refine_ls_wR_factor_ref         0.0689
_reflns_Friedel_coverage         0.705
_reflns_Friedel_fraction_full    0.826
_reflns_Friedel_fraction_max     0.787
_reflns_number_gt                2746
_reflns_number_total             3051
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol6b03692_si_002.cif
_cod_data_source_block           ca111015_1_1_01
_cod_depositor_comments          'Adding full bibliography for 1545169.cif.'
_cod_database_code               1545169
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.985
_shelx_estimated_absorpt_t_min   0.911
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 O4-H4
 0.91 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C9(H9), C16(H16)
3.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C14(H14A,H14B)
3.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C8(H8), C10(H10), C15(H15), C18(H18)
3.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C19(H19A,H19B,H19C)
;
_shelx_res_checksum              78294
_shelx_hkl_checksum              28096
_olex2_date_sample_data_collection 2015-10-13
_olex2_date_sample_submission    2015-10-09
_olex2_submission_original_sample_id ca111015_1_1
_olex2_submission_special_instructions 'No special instructions were received'