Alkyl Phosphines as Reagents and Catalysts in Organic Synthesis

Donald H. Valentine Jr; John H. Hillhouse

doi:10.1055/s-2003-37337

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Synthesis 2003(3): 0317-0334
DOI: 10.1055/s-2003-37337

REVIEW

Alkyl Phosphines as Reagents and Catalysts in Organic Synthesis

Donald H. Valentine Jr.^a, John H. Hillhouse*^b
^a 20 Blue Ridge Rd., Ridgefield, CT 06877-2307
e-Mail: dvalentine@snet.net;
^b Cytec Canada Inc., P.O. Box 240, Niagara Falls, Ontario, L2E 6T4, Canada
e-Mail: John_Hillhouse@we.cytec.com;

Further Information

Publication History

Received 27 September 2002
Publication Date:
19 February 2003 (online)

Abstract
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Abstract

A literature review of the major stoichiometric uses of tertiary phosphines, with particular emphasis on the relative abilities of trialkylphosphines and triarylphosphines in Wittig, Staudinger, or Mitsunobu reactions, is presented. Pronounced differences in reaction rates and selectivity, product yields and ease of by-product removal are often observed when trialkylphosphines are compared with triarylphosphines as promoters in these types of reactions. Also presented here is a compilation of some useful physical properties for selected trialkylphosphines, their usual methods of preparation and typical uses in organic synthesis.

1 Introduction
2 Wittig Reaction
2.1 Staudinger Reaction
3 Hydroxyl Replacement Reaction
3.1 Mitsunobu Reaction
3.2 Tertiary Phosphines with Organosulfur and Organoselenium Compounds
3.3 Nitro Compounds and Nitriles
3.4 Reactions with Organic Halides
4 Reactions Catalyzed by Trialkylphosphines
5 Michael Reaction
6 Conclusions

Key words

phosphorus - Mitsunobu - Wittig Reactions - nucleophiles - cleavage

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11

Uses of trialkylphosphines and related reagents as ligands in catalysts for organic synthesis are discussed in Part II, manuscript in preparation.

15

Trade name CYPHOS^®3653, [i.e. trihexyl(tetradecyl)phos-phonium chloride], Cytec Industries Inc.

17

McNulty, J. Capretta, A.; Wilson, J.; Dyck, J.; Adjabeng, G.; Robertson, A. Chem. Commun. 2002, submitted for publication.

30

HP(cyclo-C₆H₁₁)₂ but not P(cyclo-C₆H₁₁)₃ can be made by free-radical addition of PH₃ to cyclohexene.