Two-Phase Terpene Total Synthesis:
Historical Perspective and Application to the Taxol® Problem

Yoshihiro Ishihara; Phil S. Baran

doi:10.1055/s-0030-1258123

ACCOUNT

Two-Phase Terpene Total Synthesis: Historical Perspective and Application to the Taxol^® Problem

Yoshihiro Ishihara, Phil S. Baran*
Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037, USA
Fax: +1(858)7847375; e-Mail: pbaran@scripps.edu;

Abstract

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Abstract

This account presents our laboratory’s latest endeavors in C_sp3−H activation in the context of total synthesis, as well as a historical perspective of the field of C_sp3−H activation. Our viewpoints in using a two-phase terpene synthesis strategy and how known oxidative transformations could benefit an eventual biomimetic synthesis of Taxol^® are discussed.

1 Introduction

2 C_sp3−H Functionalization: A Historical Perspective

3 Two-Phase Terpene Synthesis: Proof of Principle

4 A Two-Phase Approach to Taxol^®: Planning Stage

5 Heuristic Value of the Oxidation Pyramid

6 Taxol^®: Precedent and First Ruminations

7 Conclusions and Outlook

Key words

biomimetic synthesis - oxidation - pyramid - terpenoids - total synthesis

Volltext

Referenzen

References

Some reviews on C−H activation include:

<A NAME="RA56510ST-1A">1a</A> Stahl SS. Labinger JA. Bercaw JE. Angew. Chem. Int. Ed. 1998, 37: 2180

<A NAME="RA56510ST-1B">1b</A> Crabtree RH. J. Chem. Soc., Dalton Trans. 2001, 2437

<A NAME="RA56510ST-1C">1c</A> Godula K. Sames D. Science 2006, 312: 67

<A NAME="RA56510ST-1D">1d</A> Davies HML. Manning JR. Nature 2008, 451: 417

<A NAME="RA56510ST-1E">1e</A> Giri R. Shi B.-F. Engle KM. Maugel N. Yu J.-Q. Chem. Soc. Rev. 2009, 38: 3242

Representative examples include:

<A NAME="RA56510ST-2A">2a</A> Barton DHR. Beaton JM. Geller LE. Pechet MM. J. Am. Chem. Soc. 1960, 82: 2640

<A NAME="RA56510ST-2B">2b</A> Barton DHR. Beaton JM. J. Am. Chem. Soc. 1960, 82: 2641

<A NAME="RA56510ST-2C">2c</A> Barton DHR. Beaton JM. Geller LE. Pechet MM. J. Am. Chem. Soc. 1961, 83: 4076

<A NAME="RA56510ST-2D">2d</A> Akhtar M. Barton DHR. J. Am. Chem. Soc. 1964, 86: 1528

Representative examples include:

<A NAME="RA56510ST-3A">3a</A> Breslow R. Baldwin SW. J. Am. Chem. Soc. 1970, 92: 732

<A NAME="RA56510ST-3B">3b</A> Breslow R. Scholl PC. J. Am. Chem. Soc. 1971, 93: 2331

<A NAME="RA56510ST-3C">3c</A> Breslow R. Baldwin S. Flechtner T. Kalicky P. Liu S. Washburn W. J. Am. Chem. Soc. 1973, 95: 3251

<A NAME="RA56510ST-3D">3d</A> Breslow R. Corcoran RJ. Snider BB. Doll RJ. Khanna PL. Kaleya R. J. Am. Chem. Soc. 1977, 99: 905

<A NAME="RA56510ST-4">4</A> Breslow R. Yang J. Yan J. Tetrahedron 2002, 58: 653

<A NAME="RA56510ST-5">5</A> Shenvi RA. O’Malley DP. Baran PS. Acc. Chem. Res. 2009, 42: 530

<A NAME="RA56510ST-6A">6a</A> Baran PS. Maimone TJ. Richter JM. Nature 2007, 446: 404

<A NAME="RA56510ST-6B">6b</A> Young IS. Baran PS. Nature Chem. 2009, 1: 193

<A NAME="RA56510ST-7">7</A> Burns NZ. Baran PS. Hoffmann RW. Angew. Chem. Int. Ed. 2009, 48: 2854

<A NAME="RA56510ST-8">8</A> Newhouse T. Baran PS. Hoffmann RW. Chem. Soc. Rev. 2009, 38: 3010

<A NAME="RA56510ST-9">9</A> Gaich T. Baran PS. J. Org. Chem. 2010, DOI: 10.1021/jo1006812

<A NAME="RA56510ST-10">10</A> Maimone TJ. Baran PS. Nat. Chem. Biol. 2007, 3: 396

<A NAME="RA56510ST-11">11</A> This classic reaction is present in numerous undergraduate and graduate organic textbooks for example: Smith MB. March J. March’s Advanced Organic Chemistry: Reactions Mechanisms and Structure John Wiley & Sons; New York: 2001. p.894-969

<A NAME="RA56510ST-12A">12a</A> Hofmann AW. Ber. 1885, 18: 109

<A NAME="RA56510ST-12B">12b</A> Löffler K. Freytag C. Ber. 1909, 42: 3427

<A NAME="RA56510ST-13A">13a</A> Wawzonek S. Thelen PJ. J. Am. Chem. Soc. 1950, 72: 2118

<A NAME="RA56510ST-13B">13b</A> Wawzonek S. Nelson MF. Thelen PJ. J. Am. Chem. Soc. 1951, 73: 2806

<A NAME="RA56510ST-13C">13c</A> Buchschacher P. Kalvoda J. Arigoni D. Jeger O. J. Am. Chem. Soc. 1958, 80: 2905

<A NAME="RA56510ST-13D">13d</A> Wawzonek S. Culbertson TP. J. Am. Chem. Soc. 1959, 81: 3367

<A NAME="RA56510ST-14">14</A> Corey EJ. White RW. J. Am. Chem. Soc. 1958, 80: 6686

<A NAME="RA56510ST-15">15</A> Cainelli G. Mihailovic MLj. Arigoni D. Jeger O. Helv. Chim. Acta 1959, 42: 1124

<A NAME="RA56510ST-16">16</A> Breslow R. Chem. Soc. Rev. 1972, 1: 553

<A NAME="RA56510ST-17">17</A> Breslow R. Acc. Chem. Res. 1980, 13: 170

Representative examples include:

<A NAME="RA56510ST-18A">18a</A> Barton DHR. Gastiger MJ. Motherwell WB. J. Chem. Soc., Chem. Commun. 1983, 41

<A NAME="RA56510ST-18B">18b</A> Barton DHR. Bévière SD. Doller D. Tetrahedron Lett. 1991, 32: 4671

<A NAME="RA56510ST-18C">18c</A> Barton DHR. Bévière SD. Chavasiri W. Csuhai E. Doller D. Liu WG. J. Am. Chem. Soc. 1992, 114: 2147

For a review see:

<A NAME="RA56510ST-18D">18d</A> Barton DHR. Doller D. Acc. Chem. Res. 1992, 25: 504

Representative examples include:

<A NAME="RA56510ST-19A">19a</A> Breslow R. Huang Y. Zhang X. Yang J. Proc. Nat. Acad. Sci. 1997, 94: 11156

<A NAME="RA56510ST-19B">19b</A> Breslow R. Zhang X. Huang Y. J. Am. Chem. Soc. 1997, 119: 4535

<A NAME="RA56510ST-19C">19c</A> Fang Z. Breslow R. Org. Lett. 2006, 8: 251

<A NAME="RA56510ST-20A">20a</A> Sarneski JE. Michos D. Holden Thorp H. Didiuk M. Poon T. Blewitt J. Brudvig GW. Crabtree RH. Tetrahedron Lett. 1991, 32: 1153

<A NAME="RA56510ST-20B">20b</A> Wessel J. Crabtree RH. J. Mol. Catal. A: Chem. 1996, 113: 13

<A NAME="RA56510ST-20C">20c</A> Chen K. Que L. J. Am. Chem. Soc. 2001, 123: 6327

<A NAME="RA56510ST-20D">20d</A> Chen MS. White MC. Science 2007, 318: 783

<A NAME="RA56510ST-20E">20e</A> Barluenga J. González-Bobes F. González JM. Angew. Chem. Int. Ed. 2002, 41: 2556

<A NAME="RA56510ST-20F">20f</A> Crabtree RH. Mihelcic JM. Quirk JM. J. Am. Chem. Soc. 1979, 101: 7738

<A NAME="RA56510ST-20G">20g</A> Tenaglia A. Terranova E. Waegell B. Tetrahedron Lett. 1989, 30: 5271

<A NAME="RA56510ST-20H">20h</A> Murray RW. Iyanar K. Chen J. Wearing JT. Tetrahedron Lett. 1995, 36: 6415

<A NAME="RA56510ST-20I">20i</A> Lee S. Fuchs PL. J. Am. Chem. Soc. 2002, 124: 13978

<A NAME="RA56510ST-20J">20j</A> Kamata K. Yonehara K. Nakagawa Y. Uehara K. Mizuno N. Nature Chem. 2010, 2: 478

<A NAME="RA56510ST-20K">20k</A> Mello R. Fiorentino M. Fusco C. Curci R. J. Am. Chem. Soc. 1989, 111: 6749

<A NAME="RA56510ST-20L">20l</A> DesMarteau DD. Donadelli A. Montanari V. Petrov VA. Resnati G. J. Am. Chem. Soc. 1993, 115: 4897

<A NAME="RA56510ST-20M">20m</A> Brodsky BH. Du Bois J. J. Am. Chem. Soc. 2005, 127: 15391

<A NAME="RA56510ST-20N">20n</A> Moody CJ. O’Connell JL. Chem. Commun. 2000, 1311

<A NAME="RA56510ST-20O">20o</A> Kaufman MD. Grieco PA. Bougie DW. J. Am. Chem. Soc. 1993, 115: 11648

<A NAME="RA56510ST-20P">20p</A> Concepción JI. Francisco CG. Hernández R. Salazar JA. Suárez E. Tetrahedron Lett. 1984, 25: 1953

<A NAME="RA56510ST-20Q">20q</A> Chen K. Richter JM. Baran PS. J. Am. Chem. Soc. 2008, 130: 7247

<A NAME="RA56510ST-20R">20r</A> Carr K. Sutherland JK. J. Chem. Soc., Chem. Commun. 1984, 1227

<A NAME="RA56510ST-20S">20s</A> Baldwin JE. Jones RH. Najera C. Yus M. Tetrahedron 1985, 41: 699

<A NAME="RA56510ST-20T">20t</A> Kao L.-C. Sen A. J. Chem. Soc., Chem. Commun. 1991, 1242

<A NAME="RA56510ST-20U">20u</A> Dangel BD. Johnson JA. Sames D. J. Am. Chem. Soc. 2001, 123: 8149

<A NAME="RA56510ST-20V">20v</A> Desai LV. Hull KL. Sanford MS. J. Am. Chem. Soc. 2004, 126: 9542

<A NAME="RA56510ST-20W">20w</A> Giri R. Liang J. Lei J.-G. Li J.-J. Wang D.-H. Chen X. Naggar IC. Guo C. Foxman BM. Yu J.-Q. Angew. Chem. Int. Ed. 2005, 44: 7420

<A NAME="RA56510ST-20X">20x</A> Wong M.-K. Chung N.-W. He L. Wang X.-C. Yan Z. Tang Y.-C. Yang D. J. Org. Chem. 2003, 68: 6321

<A NAME="RA56510ST-20Y">20y</A> Kasuya S. Kamijo S. Inoue M. Org. Lett. 2009, 11: 3630

<A NAME="RA56510ST-20Z">20z</A> Schönecker B. Lange C. Zheldakova T. Günther W. Görls H. Vaughan G. Tetrahedron 2005, 61: 103

(aa) Suzuki K. Oldenburg PD. Que L. Angew. Chem. Int. Ed. 2008, 47: 1887

For selected reviews on C−C bond formation directly from C−H bonds, see:

<A NAME="RA56510ST-21A">21a</A> Davies HML. Beckwith REJ. Chem. Rev. 2003, 103: 2861

<A NAME="RA56510ST-21B">21b</A> Chen X. Engle KM. Wang D.-H. Yu J.-Q. Angew. Chem. Int. Ed. 2009, 48: 5094

For a review on C−B bond formation directly from C−H bonds, see:

<A NAME="RA56510ST-21C">21c</A> Mkhalid IAI. Barnard JH. Marder TB. Murphy JM. Hartwig JF. Chem. Rev. 2010, 110: 890

<A NAME="RA56510ST-22">22</A> Davis E. Croteau R. Cyclization Enzymes in the Biosynthesis of Monoterpenes Sesquiterpenes and Diterpenes, In Topics in Current Chemistry Vol. 209: Leeper FJ. Vederas JC. , Eds.; Springer-Verlag; Berlin/Heidelberg: 2000. p.53-95

<A NAME="RA56510ST-23A">23a</A> Chen K. Baran PS. Nature 2009, 459: 824

<A NAME="RA56510ST-23B">23b</A> Chen K. Ishihara Y. Morón Galán M. Baran PS. Tetrahedron 2010, 66: 4738

<A NAME="RA56510ST-24A">24a</A> Wu Q.-X. Shi Y.-P. Jia Z.-J. Nat. Prod. Rep. 2006, 23: 699

<A NAME="RA56510ST-24B">24b</A> De Marino S. Borbone N. Zollo F. Ianaro A. Di Meglio P. Iorizzi M. Planta Med. 2005, 71: 706

<A NAME="RA56510ST-24C">24c</A> Bedrossian AG. Beauchamp PS. Bernichi B. Dev V. Kitaw KZ. Rechtshaffen H. Bottini AT. Hope H. J. Essent. Oil Res. 2001, 13: 393

<A NAME="RA56510ST-24D">24d</A> Irwin MA. Geissman TA. Phytochemistry 1973, 12: 849

<A NAME="RA56510ST-24E">24e</A> Paknikar SK. Dhekne VV. Joshi GD. Indian J. Chem. 1977, 15B: 86

<A NAME="RA56510ST-24F">24f</A> Zhao P.-J. Li G.-H. Shen Y.-M. Chem. Biodiv. 2006, 3: 337

<A NAME="RA56510ST-24G">24g</A> Kim MK. Na MS. Hong JS. Jung ST. Han"guk Nonghwa Hakhoechi 1992, 35: 59

<A NAME="RA56510ST-24H">24h</A> Yukawa C. Iwabuchi H. Komemushi S. Sawabe A. J. Oleo. Sci. 2004, 53: 343

<A NAME="RA56510ST-24I">24i</A> Korthals HP. Merkel D. Muehlstaedt M. Justus Liebigs Ann. Chem. 1971, 745: 39

<A NAME="RA56510ST-25">25</A> Chen K. Eschenmoser A. Baran PS. Angew. Chem. Int. Ed. 2009, 48: 9705

<A NAME="RA56510ST-26">26</A> For the origin of the principle of divergent synthesis; see: Boger DL. Brotherton CE. J. Org. Chem. 1984, 49: 4050

<A NAME="RA56510ST-27">27</A> Wani MC. Taylor HL. Wall ME. Coggon P. McPhail AT. J. Am. Chem. Soc. 1971, 93: 2325

<A NAME="RA56510ST-28A">28a</A> Fuchs DA. Johnson RK. Cancer Treat. Rep. 1978, 62: 1219

<A NAME="RA56510ST-28B">28b</A> Schiff PB. Fant J. Horwitz SB. Nature 1979, 277: 665

<A NAME="RA56510ST-29A">29a</A> Nicolaou KC. Yang Z. Liu JJ. Ueno H. Nantermet PG. Guy RK. Claiborne CF. Renaud J. Couladouros EA. Paulvannan K. Sorensen EJ. Nature 1994, 367: 630

<A NAME="RA56510ST-29B">29b</A> Nicolaou KC. Nantermet PG. Ueno H. Guy RK. Couladouros EA. Sorensen EJ. J. Am. Chem. Soc. 1995, 117: 624

<A NAME="RA56510ST-29C">29c</A> Nicolaou KC. Liu JJ. Yang Z. Ueno H. Sorensen EJ. Claiborne CF. Guy RK. Hwang CK. Nakada M. Nantermet PG.
J. Am. Chem. Soc. 1995, 117: 634

<A NAME="RA56510ST-29D">29d</A> Nicolaou KC. Yang Z. Liu JJ. Nantermet PG. Claiborne CF. Renaud J. Guy RK. Shibayama K. J. Am. Chem. Soc. 1995, 117: 645

<A NAME="RA56510ST-29E">29e</A> Nicolaou KC. Ueno H. Liu JJ. Nantermet PG. Yang Z. Renaud J. Paulvannan K. Chadha R. J. Am. Chem. Soc. 1995, 117: 653

<A NAME="RA56510ST-29F">29f</A> Holton RA. Somoza C. Kim HB. Liang F. Biediger RJ. Boatman PD. Shindo M. Smith CC. Kim S. J. Am. Chem. Soc. 1994, 116: 1597

<A NAME="RA56510ST-29G">29g</A> Holton RA. Kim HB. Somoza C. Liang F. Biediger RJ. Boatman PD. Shindo M. Smith CC. Kim S. J. Am. Chem. Soc. 1994, 116: 1599

<A NAME="RA56510ST-29H">29h</A> Masters JJ. Link JT. Snyder LB. Young WB. Danishefsky SJ. Angew. Chem. Int. Ed. 1995, 34: 1723

<A NAME="RA56510ST-29I">29i</A> Danishefsky SJ. Masters JJ. Young WB. Link JT. Snyder LB. Magee TV. Jung DK. Isaacs RCA. Bornmann WG. Alaimo CA. Coburn CA. Di Grandi MJ. J. Am. Chem. Soc. 1996, 118: 2843

<A NAME="RA56510ST-29J">29j</A> Wender PA. Badham NF. Conway SP. Floreancig PE. Glass TE. Gränicher C. Houze JB. Jänichen J. Lee D. Marquess DG. McGrane PL. Meng W. Mucciaro TP. Mühlebach M. Natchus MG. Paulsen H. Rawlins DB. Satkofsky J. Shuker AJ. Sutton JC. Taylor RE. Tomooka K. J. Am. Chem. Soc. 1997, 119: 2755

<A NAME="RA56510ST-29K">29k</A> Wender PA. Badham NF. Conway SP. Floreancig PE. Glass TE. Houze JB. Krauss NE. Lee D. Marquess DG. McGrane PL. Meng W. Natchus MG. Shuker AJ. Sutton JC. Taylor RE.
J. Am. Chem. Soc. 1997, 119: 2757

<A NAME="RA56510ST-29L">29l</A> Shiina I. Saitoh K. Fréchard-Ortuno I. Mukaiyama T. Chem. Lett. 1998, 27: 3

<A NAME="RA56510ST-29M">29m</A> Mukaiyama T. Shiina I. Iwadare H. Saitoh M. Nishimura T. Ohkawa N. Sakoh H. Nishimura K. Tani Y.-i. Hasegawa M. Yamada K. Saitoh K. Chem. Eur. J. 1999, 5: 121

<A NAME="RA56510ST-29N">29n</A> Morihira K. Hara R. Kawahara S. Nishimori T. Nakamura N. Kusama H. Kuwajima I. J. Am. Chem. Soc. 1998, 120: 12980

<A NAME="RA56510ST-29O">29o</A> Kusama H. Hara R. Kawahara S. Nishimori T. Kashima H. Nakamura N. Morihira K. Kuwajima I. J. Am. Chem. Soc. 2000, 122: 3811

<A NAME="RA56510ST-29P">29p</A> Doi T. Fuse S. Miyamoto S. Nakai K. Sasuga D. Takahashi T. Chem. Asian J. 2006, 1: 370

For selected reviews in taxane isolation, see:

<A NAME="RA56510ST-30A">30a</A> Baloglu E. Kingston DGI. J. Nat. Prod. 1999, 62: 1448

<A NAME="RA56510ST-30B">30b</A> Hanson JR. Nat. Prod. Rep. 2000, 17: 165

<A NAME="RA56510ST-30C">30c</A> Hanson JR. Nat. Prod. Rep. 1993, 10: 159

<A NAME="RA56510ST-30D">30d</A> Miller RW. J. Nat. Prod. 1980, 43: 425

<A NAME="RA56510ST-30E">30e</A> Guéritte-Voegelein F. Guénard D. Potier P. J. Nat. Prod. 1987, 50: 9

<A NAME="RA56510ST-30F">30f</A> Shigemori H. Kobayashi J. J. Nat. Prod. 2004, 67: 245

<A NAME="RA56510ST-30G">30g</A> Shi Q.-W. Kiyota H. Chem. Biodiv. 2005, 2: 1597

<A NAME="RA56510ST-31">31</A> Koepp AE. Hezari M. Zajicek J. Vogel BS. LaFever RE. Lewis NG. Croteau R. J. Biol. Chem. 1995, 270: 8686

<A NAME="RA56510ST-32">32</A> Hefner J. Rubenstein SM. Ketchum REB. Gibson DM. Williams RM. Croteau R. Chem. Biol. 1996, 3: 479

<A NAME="RA56510ST-33">33</A> Li H. Horiguchi T. Croteau R. Williams RM. Tetrahedron 2008, 64: 6561

<A NAME="RA56510ST-34">34</A> For a general treatment on combinatorials and permutations, see: Bóna M. Combinatorics of Permutations Chapman & Hall/CRC; Boca Raton: 2004.

<A NAME="RA56510ST-35">35</A> Compound 48 (as well as 24) has been previously obtained by total synthesis: Rubenstein SM. Williams RM. J. Org. Chem. 1995, 60: 7215

<A NAME="RA56510ST-36">36</A> Corey EJ. Cheng X.-M. The Logic of Chemical Synthesis John Wiley & Sons; New York: 1989.

<A NAME="RA56510ST-37A">37a</A> Bruggink A. Schoevaart R. Kieboom T. Org. Proc. Res. Dev. 2003, 7: 622

For a recapitulation of the concepts presented in ref. 37a in the context of Taxol^®, see:

<A NAME="RA56510ST-37B">37b</A> Walji AM. MacMillan DWC. Synlett 2007, 1477

<A NAME="RA56510ST-38A">38a</A> Vazquez A. Williams RM. J. Org. Chem. 2000, 65: 7865

<A NAME="RA56510ST-38B">38b</A> Ahn YM. Vander Velde DG. Georg GI. J. Org. Chem. 2002, 67: 7140

<A NAME="RA56510ST-38C">38c</A> Baldelli E. Battaglia A. Bombardelli E. Carenzi G. Fontana G. Gambini A. Gelmi ML. Guerrini A. Pocar D. J. Org. Chem. 2003, 68: 9773

<A NAME="RA56510ST-38D">38d</A> Horiguchi T. Cheng Q. Oritani T. Tetrahedron Lett. 2000, 41: 3907

<A NAME="RA56510ST-38E">38e</A> Horiguchi T. Nagura M. Cheng Q. Oritani T. Kudo T. Heterocycles 2000, 53: 2629

<A NAME="RA56510ST-38F">38f</A> Hoemann MZ. Velde DV. Aube J. Georg GI. Jayasinghe LR. J. Org. Chem. 1995, 60: 2918

Two-Phase Terpene Total Synthesis: Historical Perspective and Application to the Taxol® Problem

Two-Phase Terpene Total Synthesis: Historical Perspective and Application to the Taxol^® Problem