Stereoselective Ring-Opening of N-tert-Butanesulfinylaziridines: Access to Acetylenic α-Amino Alcohols

Abstract

Ring-opening of enantiopure trans and cis 2,3-disubstituted ethynyl N-tert-butanesulfinylaziridines by water under acidic conditions proved to be highly regio- and diastereoselective, leading to the corresponding enantiopure anti and syn acetylenic α-amino alcohols. The regio- and stereochemistries were unambiguously determined by NOE experiments through the formation of oxazol­idinone derivatives.

amino alcohols - asymmetric synthesis - aziridines - dia­stereoselectivity - regioselectivity

References and Notes

<A NAME="RG05306ST-1">1</A> For a recent review on the ring-opening reaction of aziridines by nucleophiles, see: Hu XE. Tetrahedron  2004,  60:  2701 

For some very recent syntheses involving ring-opening of aziridines, see:

<A NAME="RG05306ST-2A">2a</A> Li P. Evans CD. Joullié MM. Org. Lett.  2005,  7:  5325 

<A NAME="RG05306ST-2B">2b</A> Dhavale DD. Kumar KSA. Chaudhari VD. Sharma T. Sabharwal SG. Prakasha Reddy J. Org. Biomol. Chem.  2005,  3:  3720 

<A NAME="RG05306ST-2C">2c</A> Cox P. Craig D. Ioannidis S. Rahn VS. Tetrahedron Lett.  2005,  46:  4687 

<A NAME="RG05306ST-2D">2d</A> Voronkov MV. Kanamarlapudi RC. Richardson P. Tetrahedron Lett.  2005,  46:  6907 

<A NAME="RG05306ST-2E">2e</A> Sureshkumar D. Koutha SM. Chandrasekaran S. J. Am. Chem. Soc.  2005,  127:  12760 

<A NAME="RG05306ST-2F">2f</A> Concellón JM. Riego E. Rivero IA. Ochoa A. J. Org. Chem.  2004,  69:  6244 

<A NAME="RG05306ST-2G">2g</A> Yun JM. Sim TB. Hahm HS. Lee WK. J. Org. Chem.  2003,  68:  7675 

<A NAME="RG05306ST-2H">2h</A> Olofsson B. Somfai P. J. Org. Chem.  2003,  68:  2514 

<A NAME="RG05306ST-2I">2i</A> Baron E. O’Brien P. Towers TD. Tetrahedron Lett.  2002,  43:  723 

<A NAME="RG05306ST-2J">2j</A> Kroutil J. Trnka T. Budesinsky M. Cerny M. Eur. J. Org. Chem.  2002,  2449 

<A NAME="RG05306ST-2K">2k</A> Paul BJ. Hobbs E. Buccino P. Hudlicky T. Tetrahedron Lett.  2001,  42:  6433 

<A NAME="RG05306ST-2L">2l</A> Armarlo S. Cardillo G. Gentilucci L. Gianotti M. Talomelli A. Org. Lett.  2000,  8:  1105 

<A NAME="RG05306ST-2M">2m</A> Fernández-Megía E. Montaos MA. Sardina FJ. J. Org. Chem.  2000,  65:  6780 

For some selected recent examples, see:

<A NAME="RG05306ST-3A">3a</A> Satoh T. Fukuda Y. Tetrahedron  2003,  59:  9803 

<A NAME="RG05306ST-3B">3b</A> Anzai M. Yanada R. Fujii N. Ohno H. Ibuka T. Takemoto Y. Tetrahedron  2002,  58:  5231 

<A NAME="RG05306ST-3C">3c</A> Crousse B. Narizuka S. Bonnet-Delpon D. Bégué J.-P. Synlett  2001,  679 

<A NAME="RG05306ST-3D">3d</A> Park J.-I. Tian GR. Kim DH. J. Org. Chem.  2001,  66:  3696 

<A NAME="RG05306ST-3E">3e</A> Papa C. Tomasini C. Eur. J. Org. Chem.  2000,  1569 

<A NAME="RG05306ST-3F">3f</A> Park CS. Choi HG. Lee H. Lee WK. Ha H.-J. Tetrahedron: Asymmetry  2000,  11:  3283 

<A NAME="RG05306ST-3G">3g</A> Wu J. Hou X.-L. Dai L.-X. J. Org. Chem.  2000,  65:  1344 

For some selected recent examples, see:

<A NAME="RG05306ST-4A">4a</A> Nadir UK. Krishna RV. Singh A. Tetrahedron Lett.  2005,  46:  479 

<A NAME="RG05306ST-4B">4b</A> Mao H. Wan B. Wang R. Wu F. Lu S. J. Org. Chem.  2004,  69:  9123 

<A NAME="RG05306ST-4C">4c</A> Hancock MT. Pinhas AR. Synlett  2004,  2347 

<A NAME="RG05306ST-4D">4d</A> Concellón JM. Riego EJ. J. Org. Chem.  2003,  68:  6407 

<A NAME="RG05306ST-4E">4e</A> Watson IDG. Yudin AK. J. Org. Chem.  2003,  68:  5160 

<A NAME="RG05306ST-4F">4f</A> Kawate T. Katagiri T. Uneyama K. Tetrahedron  2003,  59:  8939 

<A NAME="RG05306ST-4G">4g</A> Cossy J. Bellosta V. Alauze V. Desmurs J.-R. Synthesis  2002,  2211 

<A NAME="RG05306ST-5">5</A> Sabitha G. Babu RS. Rajkumar M. Reddy ChS. Yadav JS. Tetrahedron Lett.  2001,  42:  3955 

<A NAME="RG05306ST-6A">6a</A> Yadav JS. Reddy BVS. Kumar GM. Murthy ChVSR. Synth. Commun.  2002,  32:  1797 

<A NAME="RG05306ST-6B">6b</A> Yadav JS. Reddy BV. Parimala G. Reddy PV. Synthesis  2002,  2383 

<A NAME="RG05306ST-7A">7a</A> Chuang T.-H. Sharpless KB. Org. Lett.  2000,  2:  3555 

<A NAME="RG05306ST-7B">7b</A> Davoli P. Moretti I. Prati F. Alper H. J. Org. Chem.  1999,  64:  518 

<A NAME="RG05306ST-7C">7c</A> Ley SV. Middleton B. Chem. Commun.  1998,  1995 

<A NAME="RG05306ST-8">8</A> Testa L. Akssira M. Zaballos-García E. Arroyo P. Domingo LR. Sepúlveda-Arques J. Tetrahedron  2003,  59:  677 

<A NAME="RG05306ST-9A">9a</A> Joly GJ. Peeters K. Mao H. Brossette T. Hoornaert GJ. Compernolle F. Tetrahedron Lett.  2000,  41:  2223 

<A NAME="RG05306ST-9B">9b</A> Chakraborty TK. Jayaprakash S. Tetrahedron Lett.  1997,  38:  8899 

For some selected recent examples, see

<A NAME="RG05306ST-10A">10a</A> Hodgson DM. Stefane B. Miles TJ. Witherington J. Chem. Commun.  2004,  2234 

<A NAME="RG05306ST-10B">10b</A> Olofsson B. Somfai P. J. Org. Chem.  2002,  67:  8574 

<A NAME="RG05306ST-10C">10c</A> Prasad BAB. Sanghi R. Singh VK. Tetrahedron  2002,  58:  7355 

<A NAME="RG05306ST-10D">10d</A> Takemoto Y. Anzai M. Yanada R. Fujii N. Ohno H. Ibuka T. Tetrahedron Lett.  2001,  42:  1725 

<A NAME="RG05306ST-10E">10e</A> Ohno H. Hamaguchi H. Tanaka T. J. Org. Chem.  2001,  66:  1897 

<A NAME="RG05306ST-10F">10f</A> Righi G. Pietrantonio S. Bonini C. Tetrahedron  2001,  57:  10039 

<A NAME="RG05306ST-11">11</A> Howell AR. So RC. Richardson SK. Tetrahedron  2004,  60:  11327 

<A NAME="RG05306ST-12">12</A> Chemla F. Ferreira F. J. Org. Chem.  2004,  69:  8244 

<A NAME="RG05306ST-13">13</A> Ferreira F. Audouin M. Chemla F. Chem. Eur. J.  2005,  11:  5269 

<A NAME="RG05306ST-14A">14a</A> Davis FA. McCoull W. Tetrahedron Lett.  1999,  40:  249 

<A NAME="RG05306ST-14B">14b</A> Davis FA. Reddy GV. Tetrahedron Lett.  1996,  37:  4349 

<A NAME="RG05306ST-14C">14c</A> Davis FA. Zhou P. Reddy GV. J. Org. Chem.  1994,  59:  3243 

<A NAME="RG05306ST-15">15</A>

Acetylenic α-Amino Alcohols 4a-g; Typical Procedure. A stirred solution of N-tert-butanesulfinylaziridines 3a-g (1.00 mmol) and PTSA monohydrate (190 mg, 1.00 mmol) in MeCN (40 mL) and H₂O (5.7 mL) was refluxed for 20 h. After cooling to r.t., a sat. aq solution of NaHCO₃ (40 mL) and CH₂Cl₂ (40 mL) were added and the resulting mixture was stirred for 15 min at r.t. The layers were then separated and the aqueous layer was extracted with CH₂Cl₂ (3 × 40 mL). The combined organic layers were washed with a sat. aq solution of NaHCO₃ (40 mL), dried over anhyd Na₂SO₄, and concentrated in vacuo. The residual oil was purified by flash chromatography over silica gel (CH₂Cl₂ → MeOH-CH₂Cl₂, 1:9) to first give regioisomers 5a-g and then the corresponding diastereo- and enantiomerically pure acetylenic α-amino alcohols 4a-g.

<A NAME="RG05306ST-16">16</A> Bergmeier SC. Katz SJ. Huang J. McPherson H. Donoghue PJ. Reed DD. Tetrahedron Lett.  2004,  45:  5011 ; and references cited therein

<A NAME="RG05306ST-17A">17a</A> Alouane N. Boutier A. Baron C. Vrancken E. Mangeney P. Synthesis  2006,  885 

<A NAME="RG05306ST-17B">17b</A> Katakai R. Iiuzuka Y. J. Org. Chem.  1985,  50:  715