Cationic Rhodium(I)/BINAP-Type Bisphosphine Complexes: Versatile New Catalysts for Highly Chemo-, Regio-, and Enantioselective [2+2+2] Cycloadditions

Abstract

Our research group was the first to discover that cationic rhodium(I)/BINAP-type bisphosphine complexes are versatile new catalysts for highly chemo-, regio-, and enantioselective [2+2+2] cycloadditions. The high chemo- and regioselectivity of these ­cycloadditions enabled efficient catalytic synthesis of substituted benzenes, cyclophanes, and nitrogen heterocycles. Furthermore, enantioselective variants of these cycloadditions were also developed that realized efficient catalytic constructions of axial, planar, central, and spiro chirality.

1 Introduction

2 Chemo- and Regioselective [2+2+2] Cycloadditions

2.1 [2+2+2] Cycloaddition of Terminal Alkynes

2.2 [2+2+2] Cycloaddition of Two Different Alkynes

2.3 [2+2+2] Cycloaddition of α,ω-Diynes with Alkynes

2.4 [2+2+2] Cycloaddition of Alkynes with Isocyanates, Isothiocyanates, and Carbon Disulfide

2.5 [2+2+2] Cycloaddition of Alkynes with Nitriles

3 Enantioselective [2+2+2] Cycloadditions

3.1 Construction of Axial Chirality

3.2 Construction of Planar Chirality

3.3 Construction of Central Chirality

3.4 Construction of Spiro Chirality

4 Summary

alkynes - asymmetric catalysis - BINAP - cycloadditions - rhodium

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<A NAME="RA45407ST-48A">48a</A> Kitagawa O. Yoshikawa M. Tanabe H. Morita T. Takahashi M. Dobashi Y. Taguchi T. J. Am. Chem. Soc.  2006,  128:  12923 

<A NAME="RA45407ST-48B">48b</A> Kitagawa O. Takahashi M. Yoshikawa M. Taguchi T. J. Am. Chem. Soc.  2005,  127:  3676 

<A NAME="RA45407ST-48C">48c</A> Kitagawa O. Kohriyama M. Taguchi T. J. Org. Chem.  2002,  67:  8682 

<A NAME="RA45407ST-48D">48d</A> Terauchi J. Curran DP. Tetrahedron: Asymmetry  2003,  14:  587 

<A NAME="RA45407ST-49">49</A>

For RhCl(PPh₃)₃-catalyzed [2+2+2] cycloadditions involving alkynamides, see refs 11h, 11i, and 11q.

<A NAME="RA45407ST-50">50</A> Tanaka K. Takeishi K. Noguchi K. J. Am. Chem. Soc.  2006,  128:  4586 

<A NAME="RA45407ST-51">51</A> For the synthesis of racemic phosphorus-containing biaryls via the Diels-Alder reaction using phosphorus-containing dienophiles, see: Ashburn BO. Carter RG. Angew. Chem. Int. Ed.  2006,  45:  6737 

<A NAME="RA45407ST-52">52</A> Very recently, Heller and co-workers have reported the synthesis of phosphorus-bearing, axially chiral biaryls by cobalt-catalyzed, asymmetric cross-cyclotrimerization, but both yields and ee values are not sufficient, see: Heller B. Gutnov A. Fischer C. Drexler H.-J. Spannenberg A. Redkin D. Sundermann C. Sundermann B. Chem. Eur. J.  2007,  13:  1117 

<A NAME="RA45407ST-53">53</A> Nishida G. Noguchi K. Hirano M. Tanaka K. Angew. Chem. Int. Ed.  2007,  46:  3951 

<A NAME="RA45407ST-54">54</A> Buchwald and co-workers recently reported that the substituents ortho to the phosphorus center of achiral biaryl monophosphines may lock the ligand into a certain conformation, which plays an important role in the palladium-catalyzed cross-coupling reactions, see: Burgos CH. Barder TE. Huang X. Buchwald SL. Angew. Chem. Int. Ed.  2006,  45:  4321 

For reviews on cyclophanes, see:

<A NAME="RA45407ST-55A">55a</A> Modern Cyclophane Chemistry   Gleither R. Hopf H. Wiley; Chichester: 2004. 

<A NAME="RA45407ST-55B">55b</A> Cyclophane Chemistry   Vögtle F. Wiley; Chichester: 1993. 

<A NAME="RA45407ST-56">56</A> For a review on cyclophane synthesis, see: Kane VV. De Wolff WH. Bickelhaupt F. Tetrahedron  1994,  50:  4574 

<A NAME="RA45407ST-57">57</A> Wijsman GW. de Kanter FJJ. de Wolf WH. Bickelhaupt F. Eur. J. Org. Chem.  2001,  2743 

<A NAME="RA45407ST-58">58</A> Tanaka K. Sagae H. Toyoda K. Noguchi K. Hirano M. J. Am. Chem. Soc.  2007,  129:  1522 

<A NAME="RA45407ST-59">59</A>

For rhodium-catalyzed macrocyclizations to form ortho- and metacyclophanes via intramolecular [2+2+2] cycloaddition of triynes in an aqueous-organic biphasic system, see reference 11n.

For selected recent examples of the synthesis of planar-chiral [n]metacyclophanes, see:

<A NAME="RA45407ST-60A">60a</A> Piatek P. Kalisiak J. Jurczak J. Tetrahedron Lett.  2004,  45:  3309 

<A NAME="RA45407ST-60B">60b</A> Kubik S. Goddard R. J. Org. Chem.  1999,  64:  9475 

<A NAME="RA45407ST-60C">60c</A> Grimme S. Harren J. Sobanski A. Vögtle F. Eur. J. Org. Chem.  1998,  1491 

<A NAME="RA45407ST-61">61</A> Pugin B, Martin P, Mueller M, Naud F, Spindler F, Thommen M, Melone G, and Kesselgruber M. inventors; WO  2004089920. 

<A NAME="RA45407ST-62">62</A>

For examples of transesterification in metal-catalyzed [2+2+2] cycloadditions, see references 19c, 19e, and 19f.

For ruthenium-catalyzed, sequential one-pot transesterification and [2+2+2] cycloaddition of alkynylboronates, see:

<A NAME="RA45407ST-63A">63a</A> Yamamoto Y. Ishi J. Nishiyama H. Itoh K. J. Am. Chem. Soc.  2004,  126:  3712 

For its application to the synthesis of phthalides, see:

<A NAME="RA45407ST-63B">63b</A> Yamamoto Y. Ishi J. Nishiyama H. Itoh K. J. Am. Chem. Soc.  2005,  127:  9625 

<A NAME="RA45407ST-64">64</A> Tanaka K. Osaka T. Noguchi K. Hirano M. Org. Lett.  2007,  9:  1307 

<A NAME="RA45407ST-65">65</A>

For the synthesis of chiral phthalides by RhCl(PPh₃)₃-catalyzed [2+2+2] cycloadditions of ester-linked diynes with acetylene, see references 11k and 11l.

<A NAME="RA45407ST-66A">66a</A> Chan ASC. Hu W. Pai C.-C. Lau C.-P. Jiang Y. Mi A. Yan M. Sun J. Lou R. Deng J. J. Am. Chem. Soc.  1997,  119:  9570 

<A NAME="RA45407ST-66B">66b</A> Arai MA. Arai T. Sasai H. Org. Lett.  1999,  1:  1795 

<A NAME="RA45407ST-66C">66c</A> Hu A.-G. Fu Y. Xie J.-H. Zhou H. Wang L.-X. Zhou Q.-L. Angew. Chem. Int. Ed.  2002,  41:  2348 

<A NAME="RA45407ST-66D">66d</A> Xie J.-H. Wang L.-X. Fu Y. Zhu S.-F. Fan B.-M. Duan H.-F. Zhou Q.-L. J. Am. Chem. Soc.  2003,  125:  4404 

<A NAME="RA45407ST-67A">67a</A> Takahashi T. Tsutsui H. Tamura M. Kitagaki S. Nakajima M. Hashimoto S. Chem. Commun.  2001,  1604 

<A NAME="RA45407ST-67B">67b</A> Tanaka M. Takahashi M. Sakamoto E. Imai M. Matsui A. Fujio M. Sakai K. Suemune H. Tetrahedron  2001,  57:  1197 

<A NAME="RA45407ST-68">68</A> Recently Shibata and co-workers used cationic rhodium(I)/modified BINAP complexes for the enantioselective synthesis of spiro compounds, see: Tsuchikama K. Kuwata Y. Shibata T. J. Am. Chem. Soc.  2006,  128:  13686 

<A NAME="RA45407ST-69">69</A> Varela JA. Castedo L. Saá C. Org. Lett.  1999,  1:  2141 

<A NAME="RA45407ST-70">70</A> Wada A. Noguchi K. Hirano M. Tanaka K. Org. Lett.  2007,  9:  1295 

<A NAME="RA45407ST-71">71</A> For a selected recent example, see: Burkinshaw SM. Griffiths J. Towns AD. J. Mater. Chem.  1998,  8:  2677 

For our recent publications concerning cationic Rh(I)/modified-BINAP-catalyzed [2+2+2] cycloadditions, see:

<A NAME="RA45407ST-72A">72a</A> Tanaka K. Hara H. Nishida G. Hirano M. Org. Lett.  2007,  9:  1907 

<A NAME="RA45407ST-72B">72b</A> Tanaka K. Otake Y. Wada A. Hirano M. Org. Lett.  2007,  9:  2203 

<A NAME="RA45407ST-72C">72c</A> Tanaka K. Nishida G. Sagae H. Hirano M. Synlett  2007,  1426