Copper(i)-catalyzed diastereoselective hydroxytrifluoromethylation of dienes accelerated by phosphine ligands
Lu, Deng-Fu; Zhu, Cheng-Liang; Xu, Hao; Chemical Science 4 (2013) 2478–; doi:10.1039/c3sc50582k

data_1514673
_publ_section_title
;
 Copper(i)-catalyzed diastereoselective hydroxytrifluoromethylation of
 dienes accelerated by phosphine ligands
;
_journal_issue                   6
_journal_name_full               'Chemical Science'
_journal_page_first              2478
_journal_paper_doi               10.1039/c3sc50582k
_journal_volume                  4
_journal_year                    2013
_chemical_formula_moiety         'C12 H15 F3 O3'
_chemical_formula_sum            'C12 H15 F3 O3'
_chemical_formula_weight         264.24
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2013-02-21
_audit_creation_method
;
Olex2 1.2-beta
(compiled Dec 5 2012 16:17:34, GUI svn.r4385)
;
_cell_angle_alpha                111.700(2)
_cell_angle_beta                 102.333(2)
_cell_angle_gamma                93.499(2)
_cell_formula_units_Z            6
_cell_length_a                   10.4133(3)
_cell_length_b                   12.3601(4)
_cell_length_c                   16.6001(6)
_cell_measurement_reflns_used    8953
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      69.168
_cell_measurement_theta_min      2.963
_cell_volume                     1916.15(11)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_collection       'APEX2 v2011.2-4 (Bruker, 2011)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      173(2)
_diffrn_detector_area_resol_mean 512
_diffrn_measured_fraction_theta_full 0.947
_diffrn_measured_fraction_theta_max 0.933
_diffrn_measurement_device_type  'Bruker D8 diffractometer with APEX2 detector'
_diffrn_measurement_method       '\f and \w scans with a narrow frame width'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0164
_diffrn_reflns_av_unetI/netI     0.0189
_diffrn_reflns_Laue_measured_fraction_full 0.947
_diffrn_reflns_Laue_measured_fraction_max 0.933
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            17421
_diffrn_reflns_point_group_measured_fraction_full 0.947
_diffrn_reflns_point_group_measured_fraction_max 0.933
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         69.439
_diffrn_reflns_theta_min         2.963
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.094
_exptl_absorpt_correction_T_max  0.7532
_exptl_absorpt_correction_T_min  0.6562
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0463 before and 0.0311 after correction.
The Ratio of minimum to maximum transmission is 0.8712.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.374
_exptl_crystal_description       prism
_exptl_crystal_F_000             828
_exptl_crystal_size_max          0.584
_exptl_crystal_size_mid          0.341
_exptl_crystal_size_min          0.232
_refine_diff_density_max         1.337
_refine_diff_density_min         -0.887
_refine_diff_density_rms         0.097
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   2.099
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     508
_refine_ls_number_reflns         6701
_refine_ls_number_restraints     133
_refine_ls_restrained_S_all      2.213
_refine_ls_R_factor_all          0.1287
_refine_ls_R_factor_gt           0.1206
_refine_ls_shift/su_max          0.019
_refine_ls_shift/su_mean         0.003
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
w=1/[\s^2^(Fo^2^)+(0.2000P)^2^]
where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4204
_refine_ls_wR_factor_ref         0.4381
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5741
_reflns_number_total             6701
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c3sc50582k.txt
_cod_data_source_block           twin4
_cod_database_code               1514673
_olex2_refinement_description
;
1. Fixed Uiso
At 1.2 times of:
H11C of C11C, H11 of C11, H9 of C9, H2A of C2A, H4A of C4A, H5A of C5A, H6A
of C6A, H3A of C3A, H5B of C5B, H6B of C6B, H13C of C13C, H13 of C13, H2CA of
C2CA, H3CA of C3CA, H4CA of C4CA, H5CA of C5CA, H6CA of C6CA, H2BA of C2BA,
H3BA of C3BA, H4BA of C4BA, H5BA of C5BA, H6BA of C6BA, {H7B,H7A} of C7, H3CB
of C3CB, H4CB of C4CB, H5CB of C5CB, H6CB of C6CB, H2CB of C2CB, H6BB of C6BB,
H5BB of C5BB, H4BB of C4BB, H3B of C3B, H4B of C4B, H11B of C11B, H2B of C2B,
{H7BB,H7BA} of C7B, H2BB of C2BB, H9B of C9B, H3BB of C3BB, H13B of C13B,
H9C of C9C, {H7CA,H7C} of C7C
At 1.5 times of:
{H16A,H16B,H16C} of C16, {H16G,H16H,H16I} of C16B, {H16D,H16E,H16F} of C16C,
H12C of O12C, H10C of O10C, H8C of O8C, H10 of O10, H12 of O12, H8B of O8B,
H8 of O8, H10B of O10B, H12B of O12B
2. Restrained distances
C7C-C1CB ~ C7C-C1CA
with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Uanis(C1A) = Uanis(C1B)
Uanis(C2A) = Uanis(C2B)
Uanis(C3A) = Uanis(C3B)
Uanis(C4A) = Uanis(C4B)
Uanis(C5A) = Uanis(C5B)
Uanis(C6A) = Uanis(C6B)
Uanis(C1BA) = Uanis(C1BB)
Uanis(C6BA) = Uanis(C6BB)
Uanis(C5BA) = Uanis(C5BB)
Uanis(C4BA) = Uanis(C4BB)
Uanis(C3BA) = Uanis(C3BB)
Uanis(C2BA) = Uanis(C2BB)
Uanis(C1CA) = Uanis(C1CB)
Uanis(C3CB) = Uanis(C4CA)
4. Others
1-Sof(H7C)=Sof(H7C)=1-Sof(H7C)=1-Sof(H7C)=1-Sof(H7C)=1-Sof(H7C)=1-Sof(H7C)=1-
Sof(H7C)=1-Sof(H7C)=1-Sof(H7C)=1-Sof(H7C)=1-Sof(H7C)=1-Sof(H7C)=Sof(C1CA)=
Sof(C2CA)=Sof(H2CA)=Sof(C3CA)=Sof(H3CA)=Sof(C4CA)=Sof(H4CA)=Sof(C5CA)=
Sof(H5CA)=Sof(C6CA)=Sof(H6CA)
1-Sof(H7BA)=Sof(H7BA)=1-Sof(H7BA)=1-Sof(H7BA)=1-Sof(H7BA)=1-Sof(H7BA)=1-
Sof(H7BA)=1-Sof(H7BA)=1-Sof(H7BA)=1-Sof(H7BA)=1-Sof(H7BA)=1-Sof(H7BA)=1-
Sof(H7BA)=Sof(C1BA)=Sof(C2BA)=Sof(H2BA)=Sof(C3BA)=Sof(H3BA)=Sof(C4BA)=
Sof(H4BA)=Sof(C5BA)=Sof(H5BA)=Sof(C6BA)=Sof(H6BA)
1-Sof(H7A)=Sof(H7A)=1-Sof(H7A)=1-Sof(H7A)=1-Sof(H7A)=1-Sof(H7A)=1-Sof(H7A)=1-
Sof(H7A)=1-Sof(H7A)=1-Sof(H7A)=1-Sof(H7A)=1-Sof(H7A)=1-Sof(H7A)=Sof(C1A)=
Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(H4A)=Sof(C5A)=Sof(H5A)=
Sof(C6A)=Sof(H6A)
5.a Ternary CH refined with riding coordinates:
C9C(H9C), C7C(H7CA), C7C(H7C), C11C(H11C), C11(H11), C9(H9), C7B(H7BB),
C7B(H7BA), C9B(H9B), C13B(H13B), C11B(H11B), C7(H7B), C7(H7A), C13C(H13C),
C13(H13)
5.b Aromatic/amide H refined with riding coordinates:
C2BB(H2BB), C3BB(H3BB), C4BB(H4BB), C5BB(H5BB), C6BB(H6BB), C2CB(H2CB),
C3CB(H3CB), C4CB(H4CB), C5CB(H5CB), C6CB(H6CB), C2B(H2B), C3B(H3B), C4B(H4B),
C5B(H5B), C6B(H6B), C2CA(H2CA), C3CA(H3CA), C4CA(H4CA), C5CA(H5CA), C6CA(H6CA),
C2BA(H2BA), C3BA(H3BA), C4BA(H4BA), C5BA(H5BA), C6BA(H6BA), C2A(H2A),
C3A(H3A), C4A(H4A), C5A(H5A), C6A(H6A)
5.c Fitted hexagon refined as free rotating group:
C1BB(C2BB,C3BB,C4BB,C5BB,C6BB), C1CB(C2CB,C3CB,C4CB,C5CB,C6CB), C1B(C2B,C3B,
C4B,C5B,C6B), C1CA(C2CA,C3CA,C4CA,C5CA,C6CA), C1BA(C2BA,C3BA,C4BA,C5BA,C6BA),
C1A(C2A,C3A,C4A,C5A,C6A)
5.d Idealised Me refined as rotating group:
C16B(H16G,H16H,H16I), C16C(H16D,H16E,H16F), C16(H16A,H16B,H16C)
5.e Idealised tetrahedral OH refined as rotating group:
O12C(H12C), O10C(H10C), O8C(H8C), O10(H10), O12(H12), O8B(H8B), O8(H8),
O10B(H10B), O12B(H12B)
;
_shelxl_version_number           2012-9