Rh-Catalyzed Stereospecific Synthesis of Allenes from Propargylic Benzoates and Arylboronic Acids.
Ruchti, Jonathan; Carreira, Erick M.; Organic letters 18 (2016) 2174–2176; doi:10.1021/acs.orglett.6b00793

data_1555545
_publ_section_title
;
 Rh-Catalyzed Stereospecific Synthesis of Allenes from Propargylic
 Benzoates and Arylboronic Acids.
;
_journal_issue                   9
_journal_name_full               'Organic letters'
_journal_page_first              2174
_journal_page_last               2176
_journal_paper_doi               10.1021/acs.orglett.6b00793
_journal_volume                  18
_journal_year                    2016
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C24 H25 N O4'
_chemical_formula_sum            'C24 H25 N O4'
_chemical_formula_weight         391.45
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2015-10-16
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                88.9680(10)
_cell_angle_beta                 86.1080(10)
_cell_angle_gamma                66.5820(10)
_cell_formula_units_Z            4
_cell_length_a                   12.7971(3)
_cell_length_b                   12.8656(3)
_cell_length_c                   14.0933(3)
_cell_measurement_reflns_used    9836
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      66.66
_cell_measurement_theta_min      3.14
_cell_volume                     2124.21(9)
_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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 8.33
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.982
_diffrn_measured_fraction_theta_max 0.982
_diffrn_measurement_device       'kappa-stage diffractometer'
_diffrn_measurement_device_type  'Bruker Apex2 Duo (Cu)'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'double mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0261
_diffrn_reflns_av_unetI/netI     0.0255
_diffrn_reflns_Laue_measured_fraction_full 0.982
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            36886
_diffrn_reflns_point_group_measured_fraction_full 0.720
_diffrn_reflns_point_group_measured_fraction_max 0.735
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         66.748
_diffrn_reflns_theta_min         3.143
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.671
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_correction_T_min  0.6837
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0612 before and 0.0421 after correction.
The Ratio of minimum to maximum transmission is 0.9082.
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    1.224
_exptl_crystal_description       block
_exptl_crystal_F_000             832
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.273
_refine_diff_density_min         -0.201
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 3554 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.12(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1065
_refine_ls_number_reflns         11081
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0313
_refine_ls_R_factor_gt           0.0307
_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^)+(0.0548P)^2^+0.3709P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0827
_refine_ls_wR_factor_ref         0.0833
_reflns_Friedel_coverage         0.498
_reflns_Friedel_fraction_full    0.479
_reflns_Friedel_fraction_max     0.489
_reflns_number_gt                10878
_reflns_number_total             11081
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol6b00793_si_003.cif
_cod_data_source_block           cu_ca081015_1_1_0m
_cod_original_cell_volume        2124.21(8)
_cod_database_code               1555545
_shelxl_version_number           2014/6
_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
2.a Secondary CH2 refined with riding coordinates:
 C9C(H9CA,H9CB), C9A(H9AA,H9AB), C9D(H9DA,H9DB), C9B(H9BA,H9BB)
2.b Aromatic/amide H refined with riding coordinates:
 C3C(H3C), C4C(H4C), C5C(H5C), C6C(H6C), C12C(H12C), C18C(H18C), C21C(H21C),
 C22C(H22C), C3A(H3A), C4A(H4A), C5A(H5A), C6A(H6A), C12A(H12A), C18A(H18A),
 C19A(H19A), C22A(H22A), C3D(H3D), C4D(H4D), C5D(H5D), C6D(H6D), C12D(H12D),
 C18D(H18D), C19D(H19D), C22D(H22D), C3B(H3B), C4B(H4B), C5B(H5B), C6B(H6B),
 C12B(H12B), C18B(H18B), C21B(H21B), C22B(H22B)
2.c Idealised Me refined as rotating group:
 C14C(H14A,H14B,H14C), C15C(H15A,H15B,H15C), C16C(H16A,H16B,H16C), C23C(H23A,
 H23B,H23C), C24C(H24A,H24B,H24C), C14A(H14D,H14E,H14F), C15A(H15D,H15E,H15F),
 C16A(H16D,H16E,H16F), C23A(H23D,H23E,H23F), C24A(H24D,H24E,H24F), C14D(H14G,
 H14H,H14I), C15D(H15G,H15H,H15I), C16D(H16G,H16H,H16I), C23D(H23G,H23H,H23I),
 C24D(H24G,H24H,H24I), C14B(H14J,H14K,H14L), C15B(H15J,H15K,H15L), C16B(H16J,
 H16K,H16L), C23B(H23J,H23K,H23L), C24B(H24J,H24K,H24L)
;
_shelx_res_checksum              49171
_shelx_hkl_checksum              19402
_olex2_date_sample_data_collection 2015-10-13
_olex2_date_sample_submission    2015-10-09
_olex2_submission_original_sample_id c081015
_olex2_submission_special_instructions 'No special instructions were received'