A selective C-H insertion/olefination protocol for the synthesis of α-methylene-γ-butyrolactone natural products.
Lloyd, Matthew G.; D'Acunto, Mariantonietta; Taylor, Richard J. K.; Unsworth, William P.; Organic & biomolecular chemistry 14 (2016) 1641–1645; doi:10.1039/c5ob02579f

data_7154854
_publ_section_title
;
 A selective C-H insertion/olefination protocol for the synthesis of
 \a-methylene-\g-butyrolactone natural products.
;
_journal_issue                   5
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              1641
_journal_page_last               1645
_journal_paper_doi               10.1039/c5ob02579f
_journal_volume                  14
_journal_year                    2016
_chemical_formula_moiety         'C17 H32 O2 Si'
_chemical_formula_sum            'C17 H32 O2 Si'
_chemical_formula_weight         296.51
_chemical_melting_point          310.5(15)
_chemical_name_systematic
(4aSR,8SR,8aSR)-8-((tert-butyldimethylsilyl)oxy)-4a-methyloctahydronaphthalen-1(2H)-one
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
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Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
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_audit_update_record
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2015-08-28 deposited with the CCDC.
2015-12-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 117.509(5)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   23.0721(10)
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_cell_length_c                   26.2324(11)
_cell_measurement_reflns_used    4616
_cell_measurement_temperature    110.05(10)
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_cell_measurement_theta_min      7.5300
_cell_volume                     3532.4(3)
_computing_cell_refinement
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
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_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
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Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
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_diffrn_ambient_environment      N~2~
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_diffrn_measured_fraction_theta_full 0.999
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_diffrn_measurement_details
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  1 omega  -68.00   22.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
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  2 omega  -21.00   69.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
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omega____ theta____ kappa____ phi______ frames
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  5 omega   23.00  111.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
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  6 omega   23.00  111.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
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  7 omega  -15.00   75.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
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  8 omega   86.00  178.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
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  9 omega   38.00  105.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
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 10 omega   35.00   94.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -25.0000 -120.0000 59

 11 omega  100.00  178.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000   60.0000 78

 12 omega   36.00  146.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -91.0000   90.0000 110

 13 omega   36.00   92.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
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 14 omega   82.00  178.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   37.0000  150.0000 96

 15 omega   35.00   94.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -25.0000 -180.0000 59

 16 omega  -26.00   72.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
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 17 omega   33.00   78.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
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 18 omega   33.00  123.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   57.0000  -60.0000 90
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_diffrn_orient_matrix_UB_11      0.0613890000
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_diffrn_reflns_limit_k_min       -5
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_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            9587
_diffrn_reflns_point_group_measured_fraction_full 0.999
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_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         67.071
_diffrn_reflns_theta_min         3.800
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.161
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_exptl_absorpt_correction_T_min  0.887
_exptl_absorpt_correction_type   gaussian
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
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Numerical absorption correction based on gaussian integration over
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Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
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_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Chloroform/diethyl ether'
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_refine_ls_extinction_method     none
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_refine_ls_hydrogen_treatment    constr
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_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0509P)^2^+2.7755P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
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_cod_depositor_comments
;
The following automatic conversions were performed:

'_chemical_melting_point' value '309-312' was changed to '310.5(15)'
- the average value was taken and precision was estimated.

Automatic conversion script
Id: cif_fix_values 4268 2015-11-12 08:31:59Z antanas 

 Adding full bibliography for 7154852--7154854.cif.
;
_cod_database_code               7154854
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C17 H32 O2 Si'
_chemical_oxdiff_usercomment     'Matthew MGL/07/40-P'
_reflns_odcompleteness_completeness 99.83
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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 Ternary CH refined with riding coordinates:
 C1(H1), C6(H6)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B)
2.c Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C14(H14A,H14B,
 H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C)
;
_olex2_date_sample_data_collection 2015-06-23
_olex2_date_sample_submission    2015-06-19
_olex2_submission_special_instructions 'No special instructions were received'