Organolithiums in Enantioselective Additions to π* and σ* Carbon-Oxygen Electrophiles

Bernd Goldfuss

doi:10.1055/s-2005-872107

REVIEW

Organolithiums in Enantioselective Additions to π* and σ* Carbon-Oxygen Electrophiles

Bernd Goldfuss*
Universität zu Köln, Institut für Organische Chemie, Greinstrasse 4, 50939 Köln, Germany
Fax: +49(221)4705057; e-Mail: Goldfuss@uni-koeln.de;

Abstract

All articles of this category

Abstract

Mediated by chiral, non-racemic ligands, organolithiums add enantioselectively to C=O functions of carbonyl compounds (aldehydes and ketones) or cleave enantioselectively C-O units in strained ethers (epoxides and oxetanes) as well as in acetals. The achievement of high enantioselectivities is desirable and hence factors controlling these enantioselectivities are the subject of intensive research. Beneficial external influences on enantioselectivity are low temperatures, suitable solvents (e.g. dimethoxymethane, dimethyl ether) and the exclusion of salt impurities. Organolithium reagents and ligands lithiated in situ form mixed anionic aggregates, some of which can be isolated and even structurally studied. The improved understanding of the nature of such chiral organolithium aggregates provides the way to a more rational design of new enantioselective organolithium reagents.

1 Introduction

2 Additions to Aldehydes

3 Additions to Ketones

4 Additions to Epoxides and Oxetanes

5 Additions to Acetals

6 Conclusions

Key words

organolithiums - enantioselectivity - chiral ligands - carbonyl compounds - strained ethers - acetals

Full Text

References

For previous reviews, see:

1a Goldfuss B. Enantio-selective Addition of Organolithiums to C=O Groups and Ethers, In Organolithiums in Enantioselective Synthesis Hodgson DM. Springer; Heidelberg: 2003. Topics in Organometallic Chemistry, Vol. 5: 21

1b Clayden J.; Organolithiums: Selectivity for Synthesis Pergamon Press; Amsterdam: 2002.

1c Corey EJ. Cheng XM. The Logic of Chemical Synthesis Wiley; New York: 1995.

1d Huryn DM. In Comprehensive Organic Synthesis Vol. 1: Trost BM. Fleming I. Pergamon Press; Amsterdam: 1991. p.49

For quantitative assessments of nucleophilicity, see:

2a Kempf B. Hampel N. Ofial AR. Mayr H. Chem. Eur. J. 2003, 9: 2209

2b Minegishi S. Mayr H. J. Am. Chem. Soc. 2003, 125: 286

2c Mayr H. Kempf B. Ofial AR. Acc. Chem. Res. 2003, 36: 66

2d Mayr H. Patz M. Gotta MF. Ofial AR. Pure Appl. Chem. 1998, 70: 1993

3a Lithium Chemistry Sapse A.-M. Schleyer PvR. Wiley; New York: 1995.

3b Lambert C. Schleyer PvR. Angew. Chem., Int. Ed. Engl. 1994, 33: 1129 ; Angew. Chem. 1994, 106, 1187

3c Lambert C. Schleyer PvR. In Methoden der organischen Chemie (Houben-Weyl) 4th ed., Vol. E19d: Thieme; Stuttgart: 1993. p.1

3d Bauer W. Schleyer PvR. In Advances in Carbanion Chemistry Vol. 1: Snieckus V. Jai Press; Greenwich: 1992.

4a Berrisford DJ. Bolm C. Sharpless KB. Angew. Chem., Int. Ed. Engl. 1995, 34: 1059 ; Angew. Chem. 1995, 107, 1159

4b Noyori R. Kitamura M. Angew. Chem., Int. Ed. Engl. 1991, 30: 49 ; Angew. Chem. 1991, 103, 34

5 Cohen HL. Wright GF. J. Org. Chem. 1953, 18: 432

6a Allentoff N. Wright GF. J. Org. Chem. 1957, 22: 1

6b French W. Wright GF. Can. J. Chem. 1964, 42: 2474

7 Iffland DC. Davis JE. J. Org. Chem. 1977, 42: 4150

8a Basu A. Thayumanavan S. Angew. Chem., Int. Ed. Engl. 2002, 43: 716 ; Angew. Chem. 2002, 114, 740

8b Goldfuss B. Nachr. Chem. 2001, 49: 1333

8c Hoppe D. Hense T. Angew. Chem., Int. Ed. Engl. 1997, 36: 2282 ; Angew. Chem. 1997, 109, 2376

9a Noyori R. Suga S. Kawai K. Okada S. Kitamura M. Pure Appl. Chem. 1988, 60: 1597

9b Tomioka K. Synthesis 1990, 541

9c Noyori R. Asymmetric catalysis in organic synthesis Wiley; New York: 1994.

10 Juaristi E. Beck AK. Hansen J. Matt T. Mukhopadhyay T. Simson M. Seebach D. Synthesis 1993, 1271. Catalytic variants of aldol-type reactions are also possible with chiral Lewis acids or organocatalytic with proline

11a Nozaki H. Aratani T. Toraya T. Tetrahedron Lett. 1968, 38: 4097

11b Nozaki H. Aratani T. Toraya T. Noyori R. Tetrahedron 1971, 27: 905

12 Seebach D. Dörr H. Bastani B. Ehrig V. Angew. Chem., Int. Ed. Engl. 1969, 8: 982 ; Angew. Chem. 1969, 81, 1002

13a Seebach D. Kalinowski H.-O. Bastani B. Crass G. Daum H. Dörr H. DuPreez NP. Ehrig V. Langer W. Nüssler C. Oei H.-A. Schmidt M. Helv. Chim. Acta 1977, 60: 301

13b Seebach D. Oei H.-A. Daum H. Chem. Ber. 1977, 110: 2316

13c Seebach D. Langer W. Helv. Chim. Acta 1979, 62: 1701

13d Seebach D. Langer W. Helv. Chim. Acta 1979, 62: 1710

14 Seebach D. Crass G. Wilka E.-M. Hilvert D. Brunner E. Helv. Chim. Acta 1979, 62: 2695

15 Mukaiyama T. Soai K. Kobayashi S. Chem. Lett. 1978, 219

16a Soai K. Mukaiyama T. Chem. Lett. 1978, 491

16b Mukaiyama T. Soai K. Sato T. Shimizu H. Suzuki K. J. Am. Chem. Soc. 1979, 101: 1455

17 Mukaiyama T. Suzuki K. Chem. Lett. 1980, 255

18 Johnson WS. Frei B. Gopalan AS. J. Org. Chem. 1981, 46: 1512

19 Mazaleyrat J.-P. Cram DJ. J. Am. Chem. Soc. 1981, 103: 4585

20 Eleveld MB. Hogeveen H. Tetrahedron Lett. 1984, 25: 5187

21 Arvidsson PI. Hilmersson G. Davidsson . Chem. Eur. J. 1999, 5: 2348

22 Whitesell JK. Jaw B.-R. J. Org. Chem. 1981, 46: 2798

23 Colombo L. Gennari C. Poli G. Scolastico C. Tetrahedron 1982, 38: 2725

24 Alberts AH. Wynberg H. J. Am. Chem. Soc. 1989, 111: 7265

25 For an early report on the role of mixed aggregates, see: Seebach D. Amstutz R. Dunitz JD. Helv. Chim. Acta 1981, 64: 2622

26 Ye M. Logaraij S. Jackman LM. Hillegass K. Hirsh KA. Bollinger AM. Grosz AL. Tetrahedron 1994, 50: 6109

27 Kang J. Kim JI. Lee JH. Bull. Korean Chem. Soc. 1994, 15: 865

28 Enantioselective protonation and alkylation with mixed aggregates of chiral 3-aminopyrrolidine lithium amides: Flinois K. Yuan Y. Bastide C. Harrison-Marchand A. Maddaluno J. Tetrahedron 2002, 58: 4707

29 Corruble A. Valnot J.-Y. Maddaluno J. Duhamel P. Tetrahedron: Asymmetry 1997, 8: 1519

30a Corruble A. Valnot J.-Y. Maddaluno J. Duhamel P. J. Org. Chem. 1998, 63: 8266

30b For a more recent computational and experimental study, see: Corruble A. Davoust D. Desjardins S. Fressigne C. Giessner-Prettre C. Harrison-Marchand A. Houte H. Lasne M.-C. Maddaluno J. Oulyadi H. Valnot J.-Y. J. Am. Chem. Soc. 2002, 124: 15267

31 Schön M. Naef R. Tetrahedron: Asymmetry 1999, 10: 169

32 Knollmüller M. Ferencic M. Gärtner P. Tetrahedron: Asymmetry 1999, 10: 3969

33 Aspinall HC. Dwyer JLM. Greeves N. Steiner A. Organometallics 1999, 18: 1366

34 Review on RLi/ROM aggregates: Lochmann L. Eur. J. Inorg. Chem. 2000, 1115

35 McGarrity JF. Ogle CA. Brich Z. Loosli H.-R. J. Am. Chem. Soc. 1985, 107: 1810

36a Snieckus V. Chem. Rev. 1990, 90: 879

36b Hommes NJRvE. Schleyer PvR. Tetrahedron 1994, 50: 5903

36c Hommes NJRvE. Schleyer PvR. Angew. Chem., Int. Ed. Engl. 1992, 31: 755 ; Angew. Chem. 1992, 104, 768

36d Goldfuss B. Schleyer PvR. Handschuh S. Hampel F. J. Organomet. Chem. 1998, 552: 285

37 Activation via deaggregation of organolithiums by coordinating solvents (THF) or ligands (TMEDA) is frequently used in lithiations of hydrocarbons: Brandsma L. Verkruijsse H. Preparative Polar Organometallic Chemistry Springer; Heidelberg: 1987.

38a Streitwieser A. Wang DZ.-R. J. Am. Chem. Soc. 1999, 121: 6213

38b Wang DZ. Kim Y.-J. Streitwieser A. J. Am. Chem. Soc. 2000, 122: 10754

39a Novak DP. Brown TL. J. Am. Chem. Soc. 1972, 94: 3793

39b Kieft RL. Novak DP. Brown TL. J. Organomet. Chem. 1974, 77: 299

39c Eppers O. Günther H. Helv. Chim. Acta 1990, 73: 207

40 Seebach D. Angew. Chem., Int. Ed. Engl. 1988, 27: 1624 ; Angew. Chem. 1988, 100, 1685

41a Weidemann B. Seebach D. Angew. Chem., Int. Ed. Engl. 1983, 22: 40 ; Angew. Chem. 1983, 95, 12

41b Pu L. Hong-Bin Y. Chem. Rev. 2001, 101: 757

41c Seebach D. Beck AK. Imwinkelried R. Roggo S. Wonnacott A. Helv. Chim. Acta 1987, 70: 954

41d Bolm C. Hildebrand JP. Muniz K. Hermanns N. Angew. Chem., Int. Ed. Engl. 2001, 40: 3284 ; Angew. Chem. 2001, 113, 3383

41e Weber B. Seebach D. Angew. Chem., Int. Ed. Engl. 1992, 31: 84 ; Angew. Chem. 1992, 104, 96

41f Weber B. Seebach D. Tetrahedron 1994, 50: 6117

Computational analyses:

41g Rudolph J. Rasmussen T. Bolm C. Norrby P.-O. Angew. Chem., Int. Ed. Engl. 2003, 42: 3002 ; Angew. Chem. 2003, 115, 3110

41h Goldfuss B. Steigelmann M. Rominger F. Eur. J. Org. Chem. 2000, 1785

41i Goldfuss B. Steigelmann M. J. Mol. Model. 2000, 6: 166

41j Goldfuss B. Steigelmann M. Khan SI. Houk KN. J. Org. Chem. 2000, 65: 77

42 Armstrong DR. Davies RP. Raithby PR. Snaith R. Wheatley AEH. New J. Chem. 1999, 23: 499

43 Hilmersson G. Davidsson O. J. Organomet. Chem. 1995, 489: 175

44 Arvidsson PI. Ahlberg P. Hilmersson G. Chem. Eur. J. 1999, 5: 1348

45 Arvidsson PI. Davidsson . Hilmersson G. Tetrahedron: Asymmetry 1999, 10: 527

46a Granander J. Sott R. Hilmersson G. Tetrahedron 2002, 58: 4717

More recently analogue mixed lithioacetonitrile aggregates were studies by ⁶Li, ¹⁵N and ¹³C couplings:

46b Sott R. Granander J. Hilmersson G. J. Am. Chem. Soc. 2004, 126: 6798

46c Sott R. Granander J. Hilmersson G. Chem. Eur. J. 2002, 8: 2081

47 For recent studies on enantiopure and racemic lithio dimethylaminomethyl benzenes, see: Kronenburg CMP. Rijnberg E. Jastrzebski JTBH. Kooijman H. Spek AL. Koten Gv. Eur. J. Org. Chem. 2004, 153

48 Williard PG. Sun C. J. Am. Chem. Soc. 1997, 119: 11693

49 Hilmersson G. Malmros B. Chem. Eur. J. 2001, 7: 331

For catalysts based on modular fenchols, see:

50a Steigelmann M. Nisar Y. Rominger F. Goldfuss B. Chem. Eur. J. 2002, 8: 5211

50b Goldfuss B. Löschmann T. Rominger F. Chem. Eur. J. 2004, 10: 5422

51a Goldfuss B. Khan SI. Houk KN. Organometallics 1999, 18: 2927

51b Goldfuss B. Steigelmann M. Rominger F. Angew. Chem. Int. Ed. 2000, 39: 4133 ; Angew. Chem. 2000, 112, 4299

51c Goldfuss B. Steigelmann M. Rominger F. Urtel H. Chem. Eur. J. 2001, 7: 4456

51d

Goldfuss, B.; Steigelmann, M.; Rominger, F.; hitherto unpublished results.

52 Kottke T. Stalke D. Angew. Chem., Int. Ed. Engl. 1993, 32: 580 ; Angew. Chem. 1993, 105, 619

53 While the 3:1 stoichiometry of this lithium butylide phenyl fencholate is analoguous to its anisol derivative, the lack of methoxy groups gives rise to different butylide encapsulation: Goldfuss B. Steigelmann M. Löschmann T. Schilling G. Rominger F. Chem. Eur. J. 2005, 11: 4019

54 Briggs TF. Winemiller MD. Xiang B. Collum DB. J. Org. Chem. 2001, 66: 6291

55 Sun X. Winemiller MD. Xiang B. Collum DB. J. Am. Chem. Soc. 2001, 123: 8039

56 Jiang B. Feng Y. Tetrahedron Lett. 2002, 43: 2975

57a Tzalis D. Knochel P. Angew. Chem., Int. Ed. Engl. 1999, 38: 1463 ; Angew. Chem. 1999, 111, 1547

57b Frantz DE. Fässler R. Carreira E. J. Am. Chem. Soc. 2000, 122: 1806

58 Corey EJ. Guzman-Perez A. Angew. Chem. Int. Ed. 1998, 37: 388 ; Angew. Chem. 1998, 110, 402

59a Organometallics in Synthesis Schlosser M. Wiley; New York: 2002. p.1

59b Wakefield BJ. In The Chemistry of Organolithium Compounds Pergamon Press; Oxford: 1974. p.129

60a Thompson A. Corley EG. Huntington MF. Grabowski EJJ. Remenar JF. Collum DB. J. Am. Chem. Soc. 1998, 120: 2028

60b Pierce ME. Parsons RL. Radesca LA. Lo YS. Silverman S. Moore JR. Islam Q. Choudhury A. Fortunak JMD. Nguyen D. Luo C. Morgan SJ. Davis WP. Confalone PN. Chen C.-Y. Tillyer RD. Frey L. Tan L. Xu F. Zhao D. Thompson AS. Corley EG. Grabowski EJJ. Reamer R. Reider PJ. J. Org. Chem. 1998, 63: 8536

For recent studies on lithium acetylide additions to quinazolinones, see:

60c Briggs TF. Winemiller MD. Collum DB. Parson RL. Davulcu AH. Harris GD. Fortunak JM. Confalone PN. J. Am. Chem. Soc. 2004, 126: 5427

61 Choudhury A. Moore JR. Pierce ME. Fortunak JM. Valvis I. Confalone PN. Org. Process Res. Dev. 2003, 7: 324

62 Thompson AS. Corley EG. Huntington MF. Grabowski EJJ. Tetrahedron Lett. 1995, 36: 8937

63a Huffman MA. Yasuda N. DeCamp AE. Grabowski EJJ. J. Org. Chem. 1995, 60: 1590

63b Parsons RL. Fortunak JM. Dorow RL. Harris GD. Kauffman GS. Nugent WA. Winemiller MD. Briggs TF. Xiang B. Collum DB. J. Am. Chem. Soc. 2001, 123: 9135

63c Rutherford JL. Hoffmann D. Collum DB. J. Am. Chem. Soc. 2002, 124: 264

64 Lucht BL. Collum DB. J. Am. Chem. Soc. 1994, 116: 7949

65 Xu F. Reamer RA. Tillyer R. Cummins JM. Grabowski EJJ. Reider PJ. Collum DB. Huffman JC. J. Am. Chem. Soc. 2000, 122: 11212

66a Ramon JD. Yus M. Tetrahedron Lett. 1998, 39: 1239

66b Dosa PI. Fu GC. J. Am. Chem. Soc. 1998, 120: 445

67 Tan L. Chen C.-Y. Tillyer RD. Grabowski EJJ. Reider PJ. Angew. Chem. Int. Ed. 1999, 38: 711 ; Angew. Chem. 1999, 111, 724

68 For a computational study, see: Banks HD. J. Org. Chem. 2003, 68: 2639

69 Lewis Acids in Organic Synthesis Yamamoto H. Wiley-VCH; Weinheim: 2000.

70 Schneider C. Brauner J. Eur. J. Org. Chem. 2001, 4445

71 Yamaguchi M. Hirao I. Tetrahedron Lett. 1983, 24: 391

72 Hodgson DM. Gibbs AR. Lee GP. Tetrahedron 1996, 52: 14361

73a Mizuno M. Kanai M. Iida A. Tomioka K. Tetrahedron: Asymmetry 1996, 7: 2483

73b Mizuno M. Kanai M. Iida A. Tomioka K. Tetrahedron 1997, 53: 19699

74 Alexakis A. Vrancken E. Mangeney P. Synlett 1998, 1165

75 Alexakis A. Vrancken E. Mangeney P. J. Chem. Soc., Perkin Trans. 1 2000, 3354

76 Oguni N. Miyagi Y. Itoh K. Tetrahedron Lett. 1998, 39: 9023

77a Seebach D. Imwinkelried R. Weber T. In Modern Synthetic Methods Vol. 4: Scheffold R. Springer; Heidelberg: 1986. p.125

77b Alexakis A. Mhamdi F. Lagasse F. Mangeney P. Tetrahedron: Asymmetry 1996, 7: 3343

For oxazaborolidinone-mediated enantioselective ring-cleavage of acetals with weaker nucleophiles, see:

78a Harada T. Egusa T. Igarashi Y. Kinugasa M. Oku A. J. Org. Chem. 2002, 67: 7080

78b Harada T. Imai K. Oku A. Synlett 2002, 972

79a Kinugasa M. Harada T. Oku A. J. Org. Chem. 1996, 61: 6772

79b Kinugasa M. Harada T. Oku A. Tetrahedron Lett. 1998, 39: 4529

80 Müller P. Nury P. Org. Lett. 2000, 2: 2845

81 Müller P. Nury P. Bernardinelli G. Eur. J. Org. Chem. 2001, 4137

82 For recent accounts on enantioselective organolithium bases, see for example Ref. 8c, and contributions in Organolithiums in Enantioselective Synthesis, Topics in Organometallic Chemistry, Vol. 5 Hodgson DM. Springer; Heidelberg: 2003.