Scope and Mechanistic Analysis of the Enantioselective Synthesis of Allenes by Rhodium-Catalyzed Tandem Ylide Formation/[2,3]-Sigmatropic Rearrangement between Donor/Acceptor Carbenoids and Propargylic Alcohols
Zhanjie Li; Vyacheslav Boyarskikh; Jørn H. Hansen; Jochen Autschbach; Djamaladdin G. Musaev; Huw M. L. Davies; Journal of the American Chemical Society 134 (2012) 15497–15504; doi:10.1021/ja3061529

data_4118637
_publ_section_title
;
 Scope and Mechanistic Analysis of the Enantioselective Synthesis of
 Allenes by Rhodium-Catalyzed Tandem Ylide Formation/[2,3]-Sigmatropic
 Rearrangement between Donor/Acceptor Carbenoids and Propargylic Alcohols
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              15497
_journal_page_last               15504
_journal_paper_doi               10.1021/ja3061529
_journal_volume                  134
_journal_year                    2012
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C27 H30 O3'
_chemical_formula_sum            'C27 H30 O3'
_chemical_formula_weight         402.51
_space_group_IT_number           19
_symmetry_cell_setting           orthorhombic
_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
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   5.7202(2)
_cell_length_b                   14.8351(6)
_cell_length_c                   26.7155(11)
_cell_measurement_reflns_used    9692
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      68.49
_cell_measurement_theta_min      2.98
_cell_volume                     2267.07(15)
_computing_cell_refinement       'Bruker SMART'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      173(2)
_diffrn_measured_fraction_theta_full 0.964
_diffrn_measured_fraction_theta_max 0.964
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0177
_diffrn_reflns_av_sigmaI/netI    0.0121
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            20515
_diffrn_reflns_theta_full        69.36
_diffrn_reflns_theta_max         69.36
_diffrn_reflns_theta_min         3.31
_exptl_absorpt_coefficient_mu    0.593
_exptl_absorpt_correction_T_max  0.9174
_exptl_absorpt_correction_T_min  0.7399
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   sadabs
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.179
_exptl_crystal_description       needle
_exptl_crystal_F_000             864
_exptl_crystal_size_max          0.54
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.131
_refine_diff_density_min         -0.193
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.06(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     271
_refine_ls_number_reflns         4004
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0305
_refine_ls_R_factor_gt           0.0298
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0445P)^2^+0.3063P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0754
_refine_ls_wR_factor_ref         0.0761
_reflns_number_gt                3924
_reflns_number_total             4004
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja3061529_si_003.cif
_cod_data_source_block           l2j_xi_84s
_cod_depositor_comments
;
The following automatic conversions were performed:

'_chemical_absolute_configuration' value 'AD' changed to 'ad'
according to the built-in table from CIF Core dictionary named
'cif_core.dic' version 2.4.1 from 2010-06-29.

Automatic conversion script
Id: cif_fix_values 1715 2011-07-08 13:25:40Z adriana 
;
_cod_database_code               4118637