SmCp<sup>R</sup><sub>2</sub>-mediated cross-coupling of allyl and propargyl ethers with ketoesters and a telescoped approach to complex cycloheptanols.
Plesniak, Mateusz P.; Just-Baringo, Xavier; Ortu, Fabrizio; Mills, David P.; Procter, David J.; Chemical communications (Cambridge, England) 52 (2016) 13503–13506; doi:10.1039/c6cc07318b

data_7125179
_publ_section_title
;
 SmCp<sup>R</sup><sub>2</sub>-mediated cross-coupling of allyl and
 propargyl ethers with ketoesters and a telescoped approach to complex
 cycloheptanols.
;
_journal_issue                   92
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              13503
_journal_page_last               13506
_journal_paper_doi               10.1039/c6cc07318b
_journal_volume                  52
_journal_year                    2016
_chemical_formula_moiety         'C44 H50 O2 Si2 Sm'
_chemical_formula_sum            'C44 H50 O2 Si2 Sm'
_chemical_formula_weight         817.37
_chemical_properties_physical    ', Air-sensitive,Moisture-sensitive'
_space_group_crystal_system      tetragonal
_space_group_IT_number           82
_space_group_name_Hall           'I -4'
_space_group_name_H-M_alt        'I -4'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-04-04
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2016-08-29 deposited with the CCDC.
2016-10-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.1871(2)
_cell_length_b                   13.1871(2)
_cell_length_c                   11.4268(4)
_cell_measurement_reflns_used    4250
_cell_measurement_temperature    150.03(10)
_cell_measurement_theta_max      23.6050
_cell_measurement_theta_min      3.8770
_cell_modulation_dimension       3
_cell_volume                     1987.12(8)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.03(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0714
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
  1 omega  -50.00  -20.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8601  -57.0000   30.0000 30

  2 omega   -8.00   56.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8601  -99.0000    0.0000 64

  3 omega  -51.00   49.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8601  -77.0000  150.0000 100

  4 omega   -1.00   89.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8601   77.0000   60.0000 90

  5 omega   -7.00   81.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8601   77.0000  -90.0000 88

  6 omega   62.00   87.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       18.8601   57.0000 -180.0000 25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0320089000
_diffrn_orient_matrix_UB_12      -0.0387637000
_diffrn_orient_matrix_UB_13      -0.0220230000
_diffrn_orient_matrix_UB_21      0.0165589000
_diffrn_orient_matrix_UB_22      0.0110225000
_diffrn_orient_matrix_UB_23      -0.0577083000
_diffrn_orient_matrix_UB_31      0.0399422000
_diffrn_orient_matrix_UB_32      -0.0356019000
_diffrn_orient_matrix_UB_33      0.0061941000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0486
_diffrn_reflns_av_unetI/netI     0.0478
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            7156
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.233
_diffrn_reflns_theta_max         25.233
_diffrn_reflns_theta_min         3.566
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.572
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65173
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.366
_exptl_crystal_description       block
_exptl_crystal_F_000             840
_exptl_crystal_size_max          0.173
_exptl_crystal_size_mid          0.0974
_exptl_crystal_size_min          0.0956
_refine_diff_density_max         1.736
_refine_diff_density_min         -1.423
_refine_diff_density_rms         0.235
_refine_ls_abs_structure_details
;
 Flack x determined using 850 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.033(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.101
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     187
_refine_ls_number_reflns         1808
_refine_ls_number_restraints     273
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.0729
_refine_ls_R_factor_gt           0.0729
_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^)+(0.1622P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1842
_refine_ls_wR_factor_ref         0.1842
_reflns_Friedel_coverage         0.891
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                1808
_reflns_number_total             1808
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6cc07318b2.cif
_cod_data_source_block           5e
_cod_original_cell_volume        1987.12(9)
_cod_database_code               7125179
_manchester_internal_coll_name   adpm148
_manchester_internal_coll_client FO/MP/DJP/DPM
_manchester_internal_coll_type   custom
_manchester_internal_coll_frame_time 5s
_manchester_internal_coll_frame_width 1
_manchester_internal_coll_frame_method '\w scans'
_manchester_internal_coll_user   FO/MP
_manchester_internal_coll_date   05/03/2015
_manchester_internal_process_user FO
_manchester_internal_process_date 16/03/2015
_manchester_internal_solution_user FO
_manchester_internal_solution_date 16/03/2015
_manchester_internal_refinement_user FO
_manchester_internal_refinement_date 04/04/2016
_manchester_internal_validation_user FO
_manchester_internal_validation_date 04/04/2016
_manchester_internal_archive_date 04/04/2016
_chemical_oxdiff_formula         'C40 Sm O2 Si2'
_reflns_odcompleteness_completeness 99.52
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.47(16) 0.53(16)
2. 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
3. Restrained distances
 C19-C20 = O1-C19 = C21-C20
 1.52 with sigma of 0.02
 C21-O1
 2.292 with sigma of 0.02
 C20-O1
 2.406 with sigma of 0.02
 C19-C21
 2.406 with sigma of 0.02
 Sm1-O1
 2.85 with sigma of 0.02
 C19-Sm1
 3.3 with sigma of 0.02
 C22-O1 = C22-C21
 1.45 with sigma of 0.02
 C22-C20
 2.385 with sigma of 0.02
 C19-C22
 2.385 with sigma of 0.02
 C14-Si1 \\sim Si1-C18
 with sigma of 0.02
 Sm1-C22 \\sim Sm1-C19
 with sigma of 0.02
4. Rigid bond restraints
 O1, C19, C20, C21, C22
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.008
5. Uiso/Uaniso restraints and constraints
Uanis(C15) \\sim Ueq: with sigma of 0.004 and sigma for terminal atoms of 0.004
Uanis(C20) \\sim Ueq: with sigma of 0.008 and sigma for terminal atoms of 0.008
Uanis(C6) \\sim Ueq: with sigma of 0.004 and sigma for terminal atoms of 0.004
Uanis(C22) \\sim Ueq: with sigma of 0.004 and sigma for terminal atoms of 0.004
Uanis(C8) \\sim Ueq, Uanis(C18) \\sim Ueq: with sigma of 0.008 and sigma for
terminal atoms of 0.008
Uanis(C21) \\sim Ueq: with sigma of 0.004 and sigma for terminal atoms of 0.004
6. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Fixed Sof: Si1(0.5) C5(0.5) H5(0.5) C1(0.5) C2(0.5) H2(0.5) C3(0.5) H3(0.5)
 C4(0.5) H4(0.5) C6(0.5) H6A(0.5) H6B(0.5) H6C(0.5) O1(0.5) C19(0.5) H19A(0.5)
 H19B(0.5) C20(0.5) H20A(0.5) H20B(0.5) C21(0.5) H21A(0.5) H21B(0.5) C22(0.5)
 H22A(0.5) H22B(0.5) C10(0.5) H10(0.5) C11(0.5) H11(0.5) C12(0.5) H12(0.5)
 C7(0.5) C8(0.5) H8(0.5) C9(0.5) H9(0.5) C13(0.5) C18(0.5) H18(0.5) C17(0.5)
 H17(0.5) C16(0.5) H16(0.5) C15(0.5) H15(0.5) C14(0.5) H14(0.5)
8.a Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B)
8.b Me refined with riding coordinates:
 C6(H6A,H6B,H6C)
8.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C2(H2), C3(H3), C4(H4), C10(H10), C11(H11), C12(H12), C8(H8), C9(H9),
 C18(H18), C17(H17), C16(H16), C15(H15), C14(H14)
8.d Fitted pentagon refined as free rotating group:
 C5(C1,C2,C3,C4)
8.e Fitted hexagon refined as free rotating group:
 C10(C11,C12,C7,C8,C9), C13(C18,C17,C16,C15,C14)
;
_shelx_res_checksum              76899
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'